U.S. patent application number 13/348603 was filed with the patent office on 2012-07-19 for coating forming composition used for forming transparent conductive film.
This patent application is currently assigned to JNC CORPORATION. Invention is credited to Setsuo Itami, Yasuhiro Kondo, Keiichi Nakamoto, Motoki Yanai.
Application Number | 20120183768 13/348603 |
Document ID | / |
Family ID | 46490996 |
Filed Date | 2012-07-19 |
United States Patent
Application |
20120183768 |
Kind Code |
A1 |
Kondo; Yasuhiro ; et
al. |
July 19, 2012 |
COATING FORMING COMPOSITION USED FOR FORMING TRANSPARENT CONDUCTIVE
FILM
Abstract
A subject is to provide a material capable of obtaining a
transparent conductive film having an excellent conductivity,
optical transparency, environmental resistance, process resistance
and close contact in a single application process, and to provide a
transparent conductive film and a device element using the same.
The means is to prepare a coating forming composition containing at
least one kind of materials selected from the group of metal
nanowires and metal nanotubes as a first component, polysaccharides
and a derivative thereof as a second component, a thermosetting
resin compound as a third component, and water as a fourth
component to obtain a transparent conductive film by using the
coating.
Inventors: |
Kondo; Yasuhiro; (Chiba,
JP) ; Nakamoto; Keiichi; (Chiba, JP) ; Itami;
Setsuo; (Chiba, JP) ; Yanai; Motoki; (Chiba,
JP) |
Assignee: |
JNC CORPORATION
TOKYO
JP
|
Family ID: |
46490996 |
Appl. No.: |
13/348603 |
Filed: |
January 11, 2012 |
Current U.S.
Class: |
428/336 ;
252/512; 252/514; 977/762; 977/932 |
Current CPC
Class: |
B82Y 40/00 20130101;
B82Y 30/00 20130101; H01B 1/22 20130101; Y10T 428/265 20150115 |
Class at
Publication: |
428/336 ;
252/512; 252/514; 977/762; 977/932 |
International
Class: |
H01B 1/22 20060101
H01B001/22; B32B 15/098 20060101 B32B015/098 |
Foreign Application Data
Date |
Code |
Application Number |
Jan 13, 2011 |
JP |
2011-4519 |
Jun 7, 2011 |
JP |
2011-127165 |
Dec 21, 2011 |
JP |
2011-279719 |
Claims
1. A coating forming composition, comprising at least one kind of
materials selected from the group of metal nanowires and metal
nanotubes as a first component, at least one kind of materials
selected from the group of polysaccharides and a derivative thereof
as a second component, a compound having at least one group
selected from the group of a (block) isocyanate group, an
amineimide group, an epoxy group, an oxetanyl group, an N-methylol
group, an N-methylol ether group and an alkoxysilyl group as a
third component, and water as a fourth component.
2. The coating forming composition according to claim 1, wherein
the third component comprises a compound having the N-methylol
group or the N-methylol ether group.
3. The coating forming composition according to claim 2, wherein
the third component is a condensation product of at least one kind
of compounds shown in the following group (A) and at least one kind
of compounds shown in the following group (B): (A) formaldehyde,
paraformaldehyde and trioxane; and (B) urea, melamine and
benzoguanamine.
4. The coating forming composition according to claim 3, wherein
the third component is a condensation product of formaldehyde and
melamine.
5. The coating forming composition according to claim 4, wherein
the third component comprises a compound having the N-methylol
ether group.
6. The coating forming composition according to claim 1, wherein
the third component comprises a compound having the alkoxysilyl
group.
7. The coating forming composition according to claim 6, wherein
the compound having the alkoxysilyl group comprises an amino group
or an epoxy group.
8. The coating forming composition according to claim 7, wherein
the third component comprises a compound represented by the
following general formula (I) or (II): ##STR00007## wherein R
independently represents an alkyl group having 1 to 3 carbons, and
n and m are independently an integer of 2 to 5.
9. The coating forming composition according to claim 6, wherein
the third component comprises a compound represented by the
following general formula (III): ##STR00008## wherein R
independently represents an alkyl group having 1 to 3 carbons, and
n is an integer of 2 to 5.
10. The coating forming composition according to claim 1, wherein
the first component comprises silver nanowires.
11. The coating forming composition according to claim 10, wherein
the first component comprises silver nanowires having a mean of
length of a minor axis in the range of 5 nanometers or more to 100
nanometers or less, and a mean of length of a major axis in the
range of 2 micrometers or more to 50 micrometers or less.
12. The coating forming composition according to claim 1, wherein
the second component comprises a cellulose ether derivative.
13. The coating forming composition according to claim 12, wherein
the second component comprises hydroxypropyl methyl cellulose.
14. The coating forming composition according to claim 1,
comprising at least one kind of compounds selected from an amine
compound, salts and metal salts of the amine compound.
15. The coating forming composition according to claim 1, wherein
the first component is in the range of 0.01% by weight or more to
1.0% by weight or less based on the total weight of the coating
forming composition, the second component is in the range of 50
parts by weight or more to 300 parts by weight or less based on 100
parts by weight of the first component, and the third component is
in the range of 1.0 part by weight or more to 50 parts by weight or
less based on 100 parts by weight of the second component.
16. The coating forming composition according to claim 1, wherein
viscosity at 25.degree. C. is in the range of 10 mPas or more to 70
mPas or less.
17. The coating forming composition according to claim 1, used for
forming a coating having conductivity.
18. A substrate having a transparent conductive film obtained using
the coating forming composition according to claim 17, wherein a
film thickness of the transparent conductive film is in the range
of 20 nanometers or more to 80 nanometers or less, a surface
resistance of the transparent conductive film is in the range of 10
.OMEGA./.quadrature. or more to 5,000 .OMEGA./.quadrature. or less,
and a total transmittance of the transparent conductive film is in
the range of 85% or more.
19. A device element, using the substrate according to claim 18.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims the priority benefits of Japan
patent application serial no. 2011-4519, filed on Jan. 13, 2011,
the priority benefit of a Japan application serial no. 2011-127165,
filed on Jun. 7, 2011 and the priority benefit of a Japan
application serial no. 2011-279719, filed on Dec. 21, 2011. The
entirety of each of the above-mentioned patent applications is
hereby incorporated by reference herein and made a part of this
specification.
FIELD OF THE INVENTION
[0002] The present invention relates to a coating forming
composition. More specifically, the invention relates to a
substrate having a transparent conductive film, which has an
excellent conductivity, optical transparency, environmental
resistance and process resistance, obtained from the composition,
and a device element using the substrate.
BACKGROUND ART
[0003] A transparent conductive film is used in various fields such
as a transparent electrode for a liquid crystal display (LCD), a
plasma display panel (PDP), an organic electroluminescence element
(OLED), a photovoltaic cell (PV) and a touch panel (TP), an
anti-electrostatic discharge (ESD) film and an electromagnetic
interference (EMI) film, and is required to have (1) a low surface
resistance, (2) a high transmittance and (3) a high
reliability.
[0004] Conventionally, indium tin oxide (ITO) has been applied to
the transparent conductive film used for the transparent
electrodes.
[0005] However, indium used for ITO has involved a problem of
supply anxiety and price soaring. Moreover, a scale of
manufacturing equipment becomes large, resulting in a long
manufacturing time and a high cost because a sputtering method
needing a high vacuum is used for forming an ITO film. Furthermore,
the ITO film easily breaks by generating a crack due to a physical
stress such as bending. A polymer of a flexible substrate is
damaged because a high heat generates during the sputtering of the
ITO film. Application of the sputtering method to a substrate
provided with flexibility is difficult. Therefore, an ITO
substitute material in which the problems are solved has been
actively searched.
[0006] Consequently, as a material allowing application and film
formation without needing sputtering among kinds of "ITO substitute
material," specific examples of materials have been reported,
including (i) a polymer conductive material such as
poly(3,4-ethylenedioxythiophene)-poly(4-styrenesulfonate)
(PEDOT:PSS) (see Patent literature No. 1), (ii) a conductive
material containing metal nanowires (see Patent literature No. 2
and Non-patent literature No. 1), (iii) a conductive material
including a random network structure by fine silver particles (see
Patent literature No. 3), (iv) a conductive material containing a
conductive component having nanostructure, such as a conductive
material containing carbon nanotubes (see Patent literature No. 4),
and (v) a conductive material including a fine mesh using metal
fine wiring (see Patent literature No. 5).
[0007] However, the material disclosed in (i) has a disadvantage of
a low transmittance and a poor environmental resistance because the
conductive material includes organic molecules, the material
disclosed in (iii) has a disadvantage of a complex process because
the transparent conductive film is prepared using
self-organization, the material disclosed in (iv) has a
disadvantage of a blackish color due to the carbon nanotubes and a
reduced transmittance, and the material disclosed in (v) has a
disadvantage of impossibility of conventional process utilization
because a photographic technology is used.
[0008] Among the materials, the conductive material containing the
metal nanowires disclosed in (ii) is optimum for "ITO substitute
material" because the conductive material is reported to show a low
surface resistance and a high transmittance (see Patent literature
No. 2 and Non-patent literature No. 1, for example), and also has
flexibility.
[0009] While the ITO substitute materials are being developed,
reduction of an environmental load is also required. In recent
years, suppression of organic solvent emission is promoted by a
legal regulation and a voluntary approach by an enterprise. As one
example of the approaches, a composition using water or a mixture
of water and a water-soluble organic solvent as a solvent, the
composition having a lower environmental load, as compared with the
organic solvent, namely, an aqueous composition has been
developed.
[0010] However, water is a peculiar liquid because water has
characteristics not seen in the organic solvent, such as a large
polarity, a hydrogen-bonding capability, having active hydrogen,
and dissolving an ionic salt. Therefore, an organic compound that
can be used in an aqueous solution is limited in view of stability
in the aqueous solution, solubility to the aqueous solution, or the
like. Thus, characteristics that can be easily achieved by using an
organic solvent composition, such as dispersibility, process
resistance and environmental resistance, can not be achieved in the
aqueous composition.
[0011] Such poorness of process resistance of the aqueous
composition becomes a problem in a conventional general
manufacturing process.
[0012] For example, the transparent conductive film needs
patterning according to an application. In general, a
photolithographic method using a resist material is utilized for
patterning. The photolithographic method includes processes of
resist application, calcination, exposure, development, etching and
peeling, and actually includes suitable substrate surface
treatment, cleaning and drying processes before and after each
process. In particular, the cleaning process is essential to an
application to an electronic material or the like for preventing a
particulate impurity, dirt and dust from depositing or entraining
onto a substrate surface.
[0013] A coating formed using the aqueous composition is prepared
using a compound easily dissolvable in water. Therefore,
dissolution, peeling and so forth of the film occur particularly in
a process using the aqueous solution, namely, the development,
etching, peeling and cleaning processes. Furthermore, deterioration
of characteristics of the coating occurs under a high temperature
and a high humidity, and thus the coating has no sufficient
environmental resistance.
[0014] The film forming composition as described in Patent
literature No. 2 is considered to have a poor process resistance.
Moreover, the transparent conductive films as described in Patent
literatures No. 6 and No. 7 are prepared by forming a transparent
conductive film using silver nanowires in a first layer, forming a
film of an organic conductive material in a second layer, and
further adding a crosslinkable compound to either one of the
layers. According to the method, the environmental resistance is
considered to be low because of the organic conductive material.
Moreover, the number of processes increases because formation of
two layers is essential.
[0015] Accordingly, an ITO substitute transparent conductive film
that is excellent in (1) conductivity, (2) optical transparency,
(3) environmental resistance and (4) process resistance, and for
which the conventional general process can be used is required.
CITATION LIST
Patent Literature
[0016] Patent literature No. 1: JP 2004-59666 A. [0017] Patent
literature No. 2: JP 2009-505358 A. [0018] Patent literature No. 3:
JP 2008-78441 A. [0019] Patent literature No. 4: JP 2007-112133 A.
[0020] Patent literature No. 5: JP 2007-270353 A. [0021] Patent
literature No. 6: JP 2010-244747 A. [0022] Patent literature No. 7:
JP 2010-205532 A.
Non-Patent Literature
[0022] [0023] Non-patent literature No. 1: Shin-Hsiang Lai,
Chun-Yao Ou, "SID 08 DIGEST," 2008, pp. 1200-1202.
SUMMARY OF INVENTION
Technical Problem
[0024] An aim of the present invention is to provide a coating
forming composition having an excellent dispersion and storage
stability in an aqueous solution by using metal nanowires or metal
nanotubes as a conductive component, and to provide a coating
having an excellent conductivity, optical transparency,
environmental resistance and process resistance in a single
application process by using the composition.
Solution to Problem
[0025] The inventors of the present invention have diligently
continued to conduct research for achieving the aims, as a result,
have found that a coating forming composition having an excellent
dispersion and storage stability in an aqueous solution is obtained
by adding a specific thermally crosslinkable resin or a compound
having an alkoxysilyl group, or both of the specific crosslinkable
resin and the compound to a composition in which metal nanowires or
metal nanotubes are dispersed, and the composition forms a
transparent conductive film having an excellent conductivity,
optical transparency, environmental resistance and process
resistance in a conventional general single application process,
and thus have completed the present invention.
[0026] As for the specific thermally crosslinkable resin included
in the present invention, thermally crosslinking a hydroxyl group
of a water-soluble polymer compound with a thermosetting resin
during calcination allows to improve environmental resistance and
process resistance of a coating.
[0027] Moreover, the compound having the alkoxysilyl group included
in the present invention forms a chemical bond with the hydroxyl
group present on an applied substrate surface during calcination,
and simultaneously has affinity with the water-soluble polymer
compound. Alternatively, the compounds thermally crosslink with
each other during calcination. The environmental resistance and the
process resistance of the coating are improved by these
functions.
[0028] The present invention concerns the following items 1 to 19,
for example.
Item 1. A coating forming composition, containing at least one kind
of materials selected from the group of metal nanowires and metal
nanotubes as a first component, at least one kind of materials
selected from the group of polysaccharides and a derivative thereof
as a second component, a compound having at least one group
selected from the group of a (block) isocyanate group, an
amineimide group, an epoxy group, an oxetanyl group, an N-methylol
group, an N-methylol ether group and an alkoxysilyl group as a
third component, and water as a fourth component. Item 2. The
coating forming composition according to item 1, wherein the third
component is a compound having the N-methylol group or the
N-methylol ether group. Item 3. The coating forming composition
according to item 2, wherein the third component is a condensation
product of at least one kind of compounds shown in the following
group (A) and at least one kind of compounds shown in the following
group (B): (A) formaldehyde, paraformaldehyde and trioxane; and (B)
urea, melamine and benzoguanamine. Item 4. The coating forming
composition according to item 3, wherein the third component is a
condensation product of formaldehyde and melamine. Item 5. The
coating forming composition according to item 4, wherein the third
component is a compound having the N-methylol ether group. Item 6.
The coating forming composition according to item 1, wherein the
third component is a compound having the alkoxysilyl group. Item 7.
The coating forming composition according to item 6, wherein the
compound having the alkoxysilyl group has an amino group or an
epoxy group. Item 8. The coating forming composition according to
item 7, wherein the third component is a compound represented by
the following general formula (I) or (II):
##STR00001##
wherein R independently represents an alkyl group having 1 to 3
carbons, and n and m are independently an integer of 2 to 5. Item
9. The coating forming composition according to item 6, wherein the
third component is a compound represented by the following general
formula (III):
##STR00002##
wherein R independently represents an alkyl group having 1 to 3
carbons, and n is an integer of 2 to 5. Item 10. The coating
forming composition according to any one of items 1 to 9, wherein
the first component is silver nanowires. Item 11. The coating
forming composition according to item 10, wherein the first
component is silver nanowires having a mean of length of a minor
axis in the range of 5 nanometers or more to 100 nanometers or
less, and a mean of length of a major axis in the range of 2
micrometers or more to 50 micrometers or less. Item 12. The coating
forming composition according to any one of items 1 to 11, wherein
the second component is a cellulose ether derivative. Item 13. The
coating forming composition according to item 12, wherein the
second component is hydroxypropyl methyl cellulose. Item 14. The
coating forming composition according to any one of items 1 to 13,
containing at least one kind of compounds selected from an amine
compound, salts and metal salts of the amine compound. Item 15. The
coating forming composition according to any one of items 1 to 14,
wherein the first component is in the range of 0.01% by weight or
more to 1.0% by weight or less based on the total weight of the
coating forming composition, the second component is in the range
of 50 parts by weight or more to 300 parts by weight or less based
on 100 parts by weight of the first component, and the third
component is in the range of 1.0 part by weight or more to 50 parts
by weight or less based on 100 parts by weight of the second
component. Item 16. The coating forming composition according to
any one of items 1 to 15, wherein viscosity at 25.degree. C. is in
the range of 10 mPas or more to 70 mPas or less. Item 17. The
coating forming composition according to any one of items 1 to 16,
used for forming a coating having conductivity. Item 18. A
substrate having a transparent conductive film obtained using the
coating forming composition according to item 17, wherein a film
thickness of the transparent conductive film is in the range of 20
nanometers or more to 80 nanometers or less, a surface resistance
of the transparent conductive film is in the range of 10
.OMEGA./.quadrature. or more to 5,000 .OMEGA./.quadrature. or less,
and a total transmittance of the transparent conductive film is in
the range of 85% or more. Item 19. A device element, using the
substrate according to item 18.
Advantageous Effects of Invention
[0029] According to the present invention, a composition in which
metal nanowires or metal nanotubes are favorably dispersed is
obtained. Moreover, a coating having an excellent conductivity,
optical transparency, environmental resistance, process resistance
and close contact can be formed by applying the composition to a
substrate in manufacturing a transparent conductive film. Moreover,
the transparent conductive film obtained can have both a low
surface resistance value and favorable optical properties such as a
favorable transmittance.
DESCRIPTION OF EMBODIMENTS
[0030] Hereinafter, the present invention will be specifically
explained.
[0031] In the specification, "transparent conductive film" means a
film having a surface resistance of approximately 10.sup.4
.OMEGA./.quadrature. or less, and a total transmittance of
approximately 80% or more. "Aqueous composition" means a
composition in which a solvent in a composition is water or a
mixture of water and a water-soluble organic solvent. "Binder" is a
resin used for allowing a conductive material of metal nanowires or
metal nanotubes to disperse in a conductive film and to support the
conductive material thereon.
1. Coating Forming Composition
[0032] A coating forming composition of the present invention
contains at least one kind of materials selected from the group of
metal nanowires and metal nanotubes as a first component
(hereinafter, referred to as the metal nanowires and the nanotubes
sometimes), at least one kind of materials selected from the group
of polysaccharides and a derivative thereof as a second component
(hereinafter, referred to as the polysaccharides and the derivative
thereof sometimes), a compound thermally crosslinking with a
hydroxyl group of the second component or a compound having an
alkoxysilyl group, or both of the compounds as a third component,
and water as a fourth component.
1-1. First Component: Metal Nanowires and Metal Nanotubes
[0033] The coating forming composition of the present invention
contains at least one kind of materials selected from the group of
metal nanowires and metal nanotubes as the first component. The
first component forms a network in a coating obtained from the
composition of the present invention and gives conductivity to the
coating.
[0034] In the specification, "metal nanowires" means a conductive
material having a wire shape, and the metal nanowires may be linear
or gently or steeply bent. Properties may be flexible or rigid.
[0035] In the specification, "metal nanotubes" means a conductive
material having a porous or nonporous tubular shape, and the metal
nanotubes may be linear or gently or steeply bent. Properties may
be flexible or rigid.
[0036] Either the metal nanowires or the metal nanotubes may be
used, or both may be mixed and used.
[0037] Specific examples of kinds of metals include at least one
kind of materials selected from the group of gold, silver,
platinum, copper, nickel, iron, cobalt, zinc, ruthenium, rhodium,
palladium, cadmium, osmium and iridium, or an alloy obtained by
combining the metals. From a viewpoint of obtaining a coating
having a low surface resistance and a high total transmittance, at
least one kind of any of gold, silver and copper is preferably
contained. The metals have a high conductivity, and therefore
density of the metal on a surface can be reduced upon obtaining a
desired surface resistance, and thus a high transmittance can be
realized. Above all, at least one kind of gold or silver is
preferably contained. As an optimum embodiment, silver is
preferred.
[0038] Length of a minor axis, length of a major axis and an aspect
ratio of the first component in the coating forming composition
have a fixed distribution. The distribution is selected from a
viewpoint where the coating obtained from the composition of the
present invention becomes high in the total transmittance and low
in the surface resistance. Specifically, a mean of the length of
the minor axis of the first component is preferably in the range of
approximately 1 nanometer or more to approximately 500 nanometers
or less, further preferably, approximately 5 nanometers or more to
approximately 200 nanometers or less, still further preferably, in
the range of approximately 5 nanometers or more to approximately
100 nanometers or less, particularly preferably, in the range of
approximately 10 nanometers or more to approximately 100 nanometers
or less. Moreover, a mean of the length of the major axis of the
first component is preferably in the range of approximately 1
micrometer or more to approximately 100 micrometers or less,
further preferably, in the range of approximately 1 micrometer or
more to approximately 50 micrometers or less, still further
preferably, approximately 2 micrometers or more to approximately 50
micrometers or less, particularly preferably, in the range of
approximately 5 micrometers or more to approximately 30 micrometers
or less. As for the first component, the mean of the length of the
minor axis and the mean of the length of the major axis meet the
ranges as described above, and a mean of the aspect ratio is
preferably approximately 1 or more, further preferably,
approximately 10 or more, still further preferably, approximately
100 or more, particularly preferably, approximately 200 or more.
Herein, the aspect ratio is a value determined by a/b when a mean
length of the minor axis and a mean length of the major axis of the
first component are approximated as b and a, respectively. Then, a
and b can be measured using a scanning electron microscope. In the
present invention, scanning electron microscope SU-70 (made by
Hitachi High-Technologies Corporation) is used.
[0039] As a method for manufacturing the first component, a known
manufacturing method can be used. For example, the silver nanowires
can be synthesized by reducing silver nitrate in the presence of
polyvinylpyrrolidone by using a polyol process (Chem. Mater., 2002,
14, 4736). Moreover, the silver nanowires can also be synthesized
by reducing silver nitrate through nucleus formation and a double
jet method without using polyvinyl pyrrolidone, as described in
Patent literature No. 5.
[0040] A diameter and length of nanowires can be controlled by
changing reaction conditions or reducing agents, or adding a salt.
The diameter and the length of nanowires are controlled by changing
reaction temperatures and reducing agents in WO 2008/073143 A. The
diameter can also be controlled by addition of potassium bromide
(ACS NANO, 2010, 4, 5, 2955).
[0041] Gold nanowires can also be synthesized by reducing
chloroaurate hydrate in the presence of polyvinylpyrrolidone in a
similar manner (J. Am. Chem. Soc., 2007, 129, 1733). A technology
for synthesizing and purifying the silver nanowires and the gold
nanowires in a large scale is described in detail in WO 2008/073143
A and WO 2008/046058 A.
[0042] Gold nanotubes having a porous structure can be synthesized
by using the silver nanowires as a mold and according to an
oxidation-reduction reaction with the silver nanowires per se by
using a chlorauric acid solution. A surface of the silver nanowires
is covered with gold according to the oxidation-reduction reaction
of silver with chloroauric acid, on the other hand, the silver
nanowires used as the mold are dissolved out into the solution, and
as a result, the gold nanotubes having the porous structure can be
prepared (J. Am. Chem. Soc., 2004, 126, 3892-3901). Moreover, the
silver nanowires as the mold can also be removed by using an
aqueous ammonia solution (ACS NANO, 2009, 3 and 6, 1365-1372).
[0043] From a viewpoint of a high conductivity and transparency,
content of the first component is preferably in the range of
approximately 0.01% by weight or more to approximately 1.0% by
weight or less, further preferably, in the range of approximately
0.05% by weight or more to approximately 0.75% by weight or less,
still further preferably, in the range of approximately 0.1% by
weight or more to approximately 0.5% by weight or less based on the
total amount of the first component to the fourth component.
1-2. Second Component: Polysaccharides and a Derivative Thereof
[0044] The coating forming composition of the present invention
contains at least one kind of materials selected from the group of
polysaccharides and a derivative thereof as the second component.
The second component provides dispersibility in a water solvent for
the first component by increasing a viscosity of the composition.
The second component forms a film and simultaneously connects the
film formed with the substrate during film formation. Moreover, the
second component plays a role of a binder. The second component is
considered to exhibit functions such as a favorable dispersibility,
a high conductivity and a high optical transparency without
adversely affecting dispersibility of the first component in the
composition, and without destroying a conductive network that the
first component of the composition of the present invention forms
in the coating obtained from the composition. Furthermore, the
hydroxyl group present in molecules of the second component
crosslinks with the third component.
[0045] Specific examples of the polysaccharides and the derivative
thereof to be used for the composition of the present invention
include polysaccharides such as starch, gum arabic, hydroxypropyl
methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose,
methyl hydroxyethyl cellulose, chitosan, dextran, guar gum and
glucomannan, and a derivative thereof. The polysaccharides and the
derivative thereof are preferably polysaccharides such as xanthan
gum, hydroxypropyl methyl cellulose, carboxymethyl cellulose,
hydroxyethyl cellulose, methyl hydroxyethyl cellulose, dextran,
guar gum and glucomannan, and a derivative thereof, further
preferably, a cellulose ether derivative such as hydroxypropyl
methyl cellulose, methyl hydroxyethyl cellulose, carboxymethyl
cellulose, methylcellulose, and ethylcellulose, particularly
preferably, hydroxypropyl methyl cellulose. In the second
component, polysaccharides having a carboxylate, sulfonate and
phosphate and a derivative thereof may be a salt of sodium,
potassium, calcium, ammonium or the like, and polysaccharides
having a nitrogen atom and a derivative thereof may have a
structure of hydrochloride, citrate or the like. The second
component can be used in one kind or in a plurality of kinds. When
using a plurality of kinds, the polysaccharides only or the
derivative thereof only, or a mixture of the polysaccharides and
the derivative thereof may be used.
[0046] As a viscosity of the polysaccharides and the derivative
thereof concerning the present invention is higher, a more uniform
dispersibility is obtained for a long period of time because
precipitation of metal nanowires and metal nanotubes is suppressed.
Furthermore, a higher conductivity is obtained because a higher
silver nanowires density with a thicker film is obtained. On the
other hand, as the viscosity is lower, smoothness and uniformity of
the coating are more satisfactory. As described above, as the
viscosity of the polysaccharides and the derivative thereof
concerning the present invention, a viscosity at 20.degree. C. of a
2.0 wt. % aqueous solution is preferably in the range of
approximately 4,000 mPas or more to approximately 1,000,000 mPas or
less, further preferably, in the range of approximately 10,000 mPas
or more to approximately 200,000 mPas or less.
[0047] For example, with regard to hydroxypropyl methyl cellulose,
weight average molecular weight is preferably in the range of
approximately 300,000 or more to approximately 3,000,000 or less,
further preferably, in the range of approximately 400,000 or more
to approximately 900,000 or less. Viscosity is proportional to
molecular weight, and when a solution of an identical concentration
is measured under identical conditions, a material having a higher
viscosity has a higher molecular weight, and a material having a
lower viscosity has a lower molecular weight.
[0048] From a viewpoint of a favorable dispersibility, a high
transmittance, film forming properties and close contact relative
to the first component in the composition, content of the second
component is preferably in the range of approximately 50 parts by
weight or more to approximately 300 parts by weight or less,
further preferably, in the range of approximately 75 parts by
weight or more to approximately 250 parts by weight or less, still
further preferably, in the range of approximately 100 parts by
weight or more to approximately 200 parts by weight or less based
on 100 parts by weight of the first component.
[0049] As a commercial product, Metolose 90SH-100000, Metolose
90SH-30000, Metolose 90SH-15000, Metolose 90SH-4000, Metolose
65SH-15000, Metolose 65SH-4000, Metolose 60SH-10000, Metolose
60SH-4000, Metolose SM-8000, Metolose SM-4000 and Metolose SHV-PF
(trade name) (made by Shin-Etsu Chemical Co., Ltd.), Methocel
K100M, Methocel K15M, Methocel K4M, Methocel F4M, Methocel E10M and
Methocel E4M (trade name) (made by the Dow Chemical Company) can be
used, for example.
1-3. Third Component
[0050] The coating forming composition of the present invention
contains the compound thermally crosslinking with the hydroxyl
group of the second component, the compound having the alkoxysilyl
group, or both of the compounds as the third component.
[0051] The third component increases physical strength of the film,
decreases water solubility and improves environmental resistance,
process resistance and close contact accompanied therewith out
adversely affecting dispersibility of the first component in the
composition and without destroying a network formed by the first
component of the composition of the present invention in the
coating obtained from the composition, and without worsening
conductivity and optical properties.
A. Compound Thermally Crosslinking with the Hydroxyl Group of the
Second Component
[0052] The compound thermally crosslinking with the hydroxyl group
of the second component reduces water solubility of the second
component and simultaneously increases physical strength of a film
by crosslinking between the second component and the third
component of the present invention during calcination. Crosslinking
uniformly exists wholly in the film, and contributes to increasing
strength. A transparent conductive film of the present invention
has one layer, and therefore peeling on a film interface does not
occur because crosslinking is more uniform, as compared with a
multilayer transparent conductive film. A decrease in water
solubility of the film by crosslinking prevents a water-soluble
solvent from penetration into the film. Thus, an etching phenomenon
of parts covered with a photoresist (referred to as under etching)
is prevented upon etching, and an applicable range (margin) of a
concentration, temperature or dipping time of an etching solution
is extended.
[0053] In addition, the compound may react with a part of hydroxy
groups without needing to react with all hydroxyl groups in the
second component.
[0054] The compound contains a thermally reactive group thermally
crosslinking with the hydroxyl group of the second component. The
compound may have one kind or a plurality of kinds of the thermally
reactive groups, furthermore, two or a plurality of the thermally
reactive groups in one molecule. Specific examples of the thermally
reactive groups include an isocyanate group, an epoxy group, an
oxetanyl group and an N-methylol group. Herein, the N-methylol
group is a functional group formed through a reaction of a compound
having at least one kind of materials selected from the group of
formaldehyde, paraformaldehyde, trioxane and hexamethylentetramine
with an amino group or an amide group, and may be etherified by any
alcohol. Moreover, the isocyanate group may be a (block) isocyanate
group prepared by protecting the isocyanate group with any alcohol
or an amineimide group as a precursor of the isocyanate group. The
compound thermally crosslinking with the hydroxyl group of the
second component is preferably a compound having a (block)
isocyanate group, an amineimide group, an epoxy group, an oxetanyl
group, an N-methylol group or an N-methylol ether group, further
preferably, a compound having a (block) isocyanate group, an epoxy
group, an N-methylol group or an N-methylol ether group, still
further preferably, a compound having an N-methylol group or an
N-methylol ether group.
[0055] As the compound having the thermally reactive group,
(meth)acrylate, (meth)acrylamide, phenolic resin, amino resin,
epoxy resin, and a precursor thereof can be used, for example.
Moreover, the compound can also be used in one kind or in a
plurality of kinds. When using the phenolic resin, amino resin,
epoxy resin or the precursor thereof, a catalyst or the like is
preferably used. The catalyst or the like as described later may be
used in one kind or a plurality of kinds. The compound thermally
crosslinking with the hydroxyl group of the second component is
preferably (meth)acrylate, (meth)acrylamide, amino resin and epoxy
resin, further preferably, amino resin, still further preferably, a
compound having N-methylol melamine or etherified N-methylol
melamine.
A-1. Phenolic Resin
[0056] As a phenolic resin that can be used as the compound
thermally crosslinking with the hydroxyl group of the second
component of the present invention, novolak resin obtained by a
condensation reaction of an aromatic compound having a phenolic
hydroxyl group with aldehydes, a homopolymer of vinylphenol
(including a hydrogenated product thereof), a vinylphenolic
copolymer of vinylphenol with a compound copolymerizable therewith
(including a hydrogenated product thereof) or the like is
preferably used.
[0057] Specific examples of the aromatic compounds having the
phenolic hydroxyl group include phenol, o-cresol, m-cresol,
p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol,
o-butylphenol, m-butylphenol, p-butylphenol, o-xylenol,
2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol,
2,3,5-trimethylphenol, 3,4,5-trimethylphenol, p-phenylphenol,
resorcinol, hydroquinone, hydroquinone monomethyl ether, a
pyrogallol, bisphenol A, bisphenol F, terpene skeleton-containing
diphenol, gallic acid, gallate, a-naphthol and .beta.-naphthol.
[0058] Specific examples of the aldehydes include formaldehyde,
paraformaldehyde, trioxane and hexamethylentetramine.
[0059] Specific examples of the compounds copolymerizable with
vinylphenol include (meth) acrylic acid or a derivative thereof,
styrene or a derivative thereof, maleic anhydride, vinyl acetate
and acrylonitrile.
[0060] As the phenolic resin, various kinds of commercial products
can be used. Specific examples include TD-4304, PE-201L and PE-602L
(trade name) (DIC, Inc.), and Shonol BRL-103, BRL-113, BRP-408A,
BRP-520, BRL-1583 and BRE-174 (trade name) (Showa Denko K.K.).
[0061] The phenolic resin may be used in one kind or in combination
of two or more kinds.
A-2. Amino Resin
[0062] An amino resin that can be used as the compound thermally
crosslinking with the hydroxyl group of the second component of the
present invention is not particularly limited, if the amino resin
is a condensation product of a compound having an aldehyde group
and a compound having an amino group or an amide group. Herein, the
compound having the aldehyde group is a compound having at least
one kind of materials selected from the group of formaldehyde,
paraformaldehyde, trioxane and hexamethylentetramine. Specific
example of the amino resins include methylol urea resin, methylol
melamine resin, etherified methylol melamine resin, benzoguanamine
resin, methylol benzoguanamine resin, etherified methylol
benzoguanamine resin and a condensation product thereof. Among the
amino resins, methylol melamine resin and etherified methylol
melamine resin are preferred in view of a favorable water
solubility at a time point before crosslinking, a favorable process
resistance and environmental resistance after film formation.
[0063] When the etherified methylol melamine resin is used as the
amino resin, a high storage stability can also be provided for the
composition. The etherified methylol melamine resin has an
excellent storage stability because of having an N-methylol ether
group that has a lower reactivity, as compared with the methylol
group. For the purpose of controlling a thermal crosslinking
reaction with the hydroxyl group of the second component, or the
like, an amino resin catalyst and a reaction initiator may be
appropriately used.
[0064] As the compound having the aldehyde group, formaldehyde,
paraformaldehyde, trioxane and hexamethylentetramine are preferred
in view of a favorable water solubility at a time point before
crosslinking, a favorable process resistance and environmental
resistance after film formation.
[0065] Specific examples of the compounds having the amino group or
the amide group include urea, melamine and benzoguanamine.
[0066] Furthermore, a combination of formaldehyde and melamine is
particularly preferred because the compound per se can work as a
corrosion inhibitor and further improve environmental resistance of
the coating.
[0067] As the amino resin, various kinds of commercial products can
be used. Specific examples include Riken Resin RG-80, Riken Resin
RG-10, Riken Resin RG-1, Riken Resin RG-1H, Riken Resin RG-85,
Riken Resin RG-83, Riken Resin RG-17, Riken Resin RG-115E, Riken
Resin RG-260, Riken Resin RG-20E, Riken Resin RS-5S, Riken Resin
RS-30, Riken Resin RS-150, Riken Resin RS-22, Riken Resin RS-250,
Riken Resin RS-296, Riken Resin HM-272, Riken Resin HM-325, Riken
Resin HM-25, Riken Resin MA-156, Riken Resin MA-100, Riken Resin
MA-31, Riken Resin MM-3C, Riken Resin MM-3, Riken Resin MM-52,
Riken Resin MM-35, Riken Resin MM-601, Riken Resin MM-630, Riken
Resin MS and Riken Resin MM-65S (trade name) (Miki Riken Industrial
Co., Ltd.), Bechamine NS-11, Bechamine LF-K, Bechamine LF-R,
Bechamine LF-55P concentrated, Bechamine NS-19, Bechamine FM-28,
Bechamine FM-7, Bechamine NS-200, Bechamine NS-210L, Bechamine
FM-180, Bechamine NF-3, Bechamine NF-12, Bechamine NF-500K,
Bechamine E, Bechamine N-13, Bechamine N-80, Bechamine J-300S,
Bechamine N, Bechamine APM, Bechamine MA-K, Bechamine MA-S,
Bechamine J-101, Bechamine J-101LF, Bechamine M-3, Bechamine
M-3(60), Bechamine A-1, Bechamine R-25H, Bechamine V-60 and
Bechamine 160 (trade name) (DIC, Inc.), Nica Resin S-176 and Nica
Resin 260 (trade name) (Nippon Carbide Industries Co., Inc.), and
Nikalac MW-30M, Nikalac MW-30, Nikalac MW-22, Nikalac MX-730,
Nikalac MX-706, Nikalac MX-035, Nikalac MX-45 and Nikalac BX-4000
(trade name) (Sanwa Chemical Co., Ltd.).
[0068] The amino resin may be used in one kind and in combination
of two or more kinds.
A-2-1. Amino Resin Catalyst and Reaction Initiator
[0069] When the coating forming composition of the present
invention contains the amino resin or the precursor, the coating
forming composition preferably contains a catalyst or a reaction
initiator in order to further improve self-hardening properties.
Specific examples of such catalysts include organic acids such as
an aromatic sulfonic acid compound and a phosphoric acid compound
and a salt thereof, an amine compound, salts of the amine compound,
an imine compound, an amidine compound, a guanidine compound, a
heterocyclic compound containing a N atom, an organometallic
compound, and metal salts such as zinc stearate, zinc myristate,
aluminum stearate and calcium stearate. Specific examples of the
reaction initiators include a photoacid generator and a photobase
generator.
[0070] The amino resin catalyst and the reaction initiator may be
used in one kind or in combination of two or more kinds. Moreover,
an amino resin catalyst and a reaction initiator based on a
different mechanism may be used.
[0071] From a viewpoint of reactivity, a favorable dispersibility
of each component in the composition, and a high conductivity, a
favorable optical transparency, a favorable environmental
resistance, a favorable process resistance and a favorable close
contact of the coating obtained from the composition of the present
invention, content of the amino resin catalyst and the reaction
initiator in the coating forming composition of the present
invention is preferably in the range of approximately 0.1 part by
weight or more to approximately 100 parts by weight or less,
further preferably, in the range of approximately 1 part by weight
or more to approximately 50 parts by weight or less, still further
preferably, in the range of approximately 5 parts by weight or more
to approximately 25 parts by weight or less based on 100 parts by
weight of the amino resin or the precursor.
[0072] As the amino resin catalyst, various kinds of commercial
products can be used. Specific examples include Riken Fixer RC,
Riken Fixer RC-3, Riken Fixer RC-12, Riken Fixer RCS, Riken Fixer
RC-W, Riken Fixer MX, Riken Fixer MX-2, Riken Fixer MX-18, Riken
Fixer MX-18N, Riken Fixer MX-36, Riken Fixer MX-15, Riken Fixer
MX-25, Riken Fixer MX-27N, Riken Fixer MX-051, Riken Fixer MX-7,
Riken Fixer DMX-5, Riken Fixer LTC-66, Riken Fixer RZ-5, Riken
Fixer XT-329, Riken Fixer XT-318, Riken Fixer XT-53, Riken Fixer
XT-58 and Riken Fixer XT-45 (trade name) (Miki Riken Industrial
Co., Ltd.), Catalyst 376, Catalyst ACX, Catalyst O, Catalyst M,
Catalyst X-80, Catalyst G, Catalyst X-60, Catalyst GT, Catalyst
X-110, Catalyst GT-3, Catalyst NFC-1 and Catalyst ML (trade name)
(DIC, Inc.), Nacure 155, Nacure 1051, Nacure 5076, Nacure 4054J,
Nacure 2500, Nacure 5225, Nacure X49-110 and Nacure 4167 (trade
name) (U.S. King Industries, Inc.).
A-2-2. Amino Resin Additive
[0073] For the purpose of improving storage stability of the amino
resin, an alcohol may be added in the range where characteristics
of the present invention are not adversely affected. Specific
examples of the alcohols that can be used for the present invention
include methanol, ethanol, isopropyl alcohol and butanol. Content
of the alcohol is preferably in the range of approximately 0.1 part
by weight or more to approximately 20 parts by weight or less,
further preferably, in the range of approximately 0.5 part by
weight or more to approximately 10 parts by weight or less, still
further preferably, in the range of approximately 1 part by weight
or more to approximately 5 parts by weight or less. The amino resin
additive may be used in one kind or in a plurality of kinds.
A-3. Epoxy Resin
[0074] In the composition of the present invention, the epoxy resin
having the epoxy group or the oxetanyl group in a molecule can be
used as the composition thermally crosslinking with the hydroxyl
group of the second component. Specific examples of the epoxy
resins include a phenol-novolak, cresol-novolak, bisphenol A,
bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F,
bisphenol S, trisphenol methane, tetraphenol ethane, bixylenol or
biphenol epoxy compound; an alicyclic or heterocyclic epoxy
compound; an epoxy compound having dicyclopentadiene or naphthalene
structure; and an epoxy compound having ethylene oxide
structure.
[0075] Moreover, specific examples of the epoxy resins include
N,N,N',N'-tetraglycidyl-m-xylenediamine,
1,3-bis(N,N-diglycidylaminomethyl)cyclohexane and
N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane.
[0076] As the epoxy resin, various kinds of commercial products can
be used for the reason of a favorable water solubility at a time
point before crosslinking and a favorable process resistance and
environmental resistance after film formation. Specific examples
include Denacol EX-614B, Denacol EX-512, Denacol EX-521, Denacol
EX-421, Denacol EX-313, Denacol EX-314, Denacol EX-810, Denacol
EX-811, Denacol EX-851, Denacol EX-821, Denacol EX-830, Denacol
EX-841, Denacol EX-832 and Denacol EX-861 (trade name) (Nagase
ChemteX Corporation).
[0077] The epoxy resin used for the composition of the present
invention may include one kind or a mixture of two or more
kinds.
A-3-1. Epoxy Curing Agent
[0078] When the coating forming composition of the present
invention contains the epoxy resin, the composition preferably
further contains an epoxy curing agent in view of further improving
a chemical resistance thereof. As the epoxy curing agent, an acid
anhydride curing agent, a polyamine curing agent, a catalyst curing
agent or the like is preferred. Moreover, an acid generator, a base
generator or the like can be used as the epoxy curing agent.
[0079] Specific examples of the acid anhydride curing agents
include maleic anhydride, tetrahydrophthalic anhydride,
hexahydrophthalic anhydride, methylhexahydrophthalic anhydride,
hexahydrotrimellitic anhydride, phthalic anhydride, trimellitic
anhydride and a styrene-maleic anhydride copolymer. Content of the
acid anhydride curing agent is preferably in the range of
approximately 1 part by weight or more to approximately 200 parts
by weight or less, further preferably, in the range of
approximately 50 parts by weight or more to approximately 150 parts
by weight or less, still further preferably, in the range of
approximately 80 parts by weight or more to approximately 120 parts
by weight or less based on 100 parts by weight of the epoxy
resin.
[0080] Specific examples of the polyamine curing agents include
diethylenetriamine, triethylenetetramine, tetraethylenepentamine,
dicyandiamide, polyamideamine (polyamide resin), a ketimine
compound, isophorone diamine, m-xylenediamine, m-phenylenediamine,
1,3-bis(aminomethyl)cyclohexane, N-aminoethylpiperazine,
4,4'-diaminodiphenylmethane,
4,4'-diamino-3,3'-diethyldiphenylmethane and
diaminodiphenylsulfone. Content of the polyamine curing agent is
preferably in the range of approximately 1 part by weight or more
to approximately 100 parts by weight or less, further preferably,
in the range of approximately 5 parts by weight or more to
approximately 80 parts by weight or less, still further preferably,
in the range of approximately 10 parts by weight or more to
approximately 50 parts by weight or less based on 100 parts by
weight of the epoxy resin.
[0081] Specific examples of the catalyst curing agents include a
tertiary amine compound and an imidazole compound. Content of the
acid catalyst curing agent is preferably in the range of
approximately 1 part by weight or more to approximately 100 parts
by weight or less, further preferably, in the range of
approximately 5 parts by weight or more to approximately 80 parts
by weight or less, still further preferably, in the range of
approximately 10 parts by weight or more to approximately 50 parts
by weight or less based on 100 parts by weight of the epoxy
resin.
[0082] The epoxy curing agent may be used in one kind or in
combination of two or more kinds.
A-4. Examples of Thermal Crosslinking with Polysaccharides and a
Derivative Thereof
[0083] An aspect of thermal crosslinking when using hydroxypropyl
methyl cellulose as the second component, and trimethylolmelamine
as the third component is schematically shown in the following
scheme (1). In addition, structure of hydroxypropyl methyl
cellulose is expressed by replacing any hydroxyl group by a methyl
ether group and a hydroxypropyl ether group in a repeating unit of
p-cellulose. The present invention is not limited to the following
scheme (1).
##STR00003##
A-5. Other Compounds Thermally Crosslinking with a Hydroxyl Group
of the Second Component
[0084] Specific examples of compounds thermally crosslinking with
the hydroxyl group of the second component, other than the phenolic
resin, the amino resin, the epoxy resin and the precursor thereof,
include a compound having a (block)isocyanate group, an activated
ester group, a carbodiimide group, an acid anhydride and an acid
halide. From a viewpoint of improvement of the environmental
resistance, the process resistance and the close contact, a
compound having a block isocyanate group is preferred. Specific
examples include Elastron BN-69, Elastron BN-37, Elastron BN-45,
Elastron BN-77, Elastron BN-04, Elastron BN-27, Elastron BN-11,
Elastron E-37, Elastron H-3, Elastron BAP, Elastron C-9, Elastron
C-52, Elastron F-29, Elastron H-38, Elastron MF-9, Elastron MF-25K,
Elastron MC, Elastron NEW BAP-15, Elastron TP-26S, Elastron W-11P,
Elastron W-22 and Elastron S-24 (trade name) (Dai-Ichi Kogyo
Seiyaku Co., Ltd.).
B. Compound Having an Alkoxysilyl Group
[0085] The compound having the alkoxysilyl group can be used as the
third component. The alkoxysilyl group has hydrolysis properties,
reacts with moisture and forms a silanol group. Then, the
alkoxysilyl group forms a hydrogen bond with a hydroxyl group
present on a surface of a substrate such as a glass, a
dehydration-condensation reaction occurs by further calcinating the
compound, and a siloxane bond being a strong covalent bond is
formed between the alkoxysilyl group and the substrate. As a
result, the close contact of a film with the substrate after
calcination can be increased. A chemical bond uniformly exists
wholly between the film and an interface of the substrate, and
contributes to an increase in close contact. Moreover, the
transparent conductive film of the present invention has one layer,
and therefore peeling on the interface of the film does not occur
because the chemical bond with the substrate can be formed, which
is different from the multilayer transparent conductive film. An
increased close contact allows to improve the environmental
resistance and the process resistance of the coating.
[0086] Moreover, the silanol group forms a siloxane oligomer by a
dehydration-condensation reaction with each other during
calcination. In the case, physical strength of the film increases
because the siloxane oligomer uniformly exists wholly in the film
in the first component or the second component. The transparent
conductive film of the present invention has one layer, and
therefore peeling on the interface of the film does not occur
because crosslinking is more uniform, as compared with the
multilayer transparent conductive film.
[0087] All of the compounds having the alkoxysilyl group may react
with the substrate or may be oligomerized. Moreover, a part may
react with the substrate, a part may be oligomerized, and a part
may be unreacted. Moreover, a plurality of siloxane bonds including
a siloxane bond with the substrate, and a siloxane bond with a
different compound having the alkoxysilyl group may be formed in
one molecule.
[0088] As the alkoxysilyl group, a methoxysilyl group, a
dimethoxysilyl group, a trimethoxysilyl group, an ethoxysilyl
group, a diethoxysilyl group, a triethoxysilyl group, a
methyldiethoxysilyl group or an ethyldimethoxysilyl group is
preferred in view of reactivity or easiness of industrial
procurement. In the case of an alkoxysilyl group having two or more
alkoxy groups, a trimethoxysilyl group, a triethoxysilyl group or a
methyldiethoxysilyl group is preferred, and a trimethoxysilyl group
or a triethoxysilyl group is most preferred because a formed
siloxane bond forms a high-dimensional crosslinking structure, and
a larger increase in cross contact and physical strength of the
film can be expected. Moreover, the compound may have one kind or a
plurality of kinds of alkoxysilyl groups, and two or more
alkoxysilyl groups in one molecule.
[0089] As the compound having the alkoxysilyl group, alkyl
alkoxysilanes, alkoxysilazanes, a silane coupling agent, a compound
having alkoxysilyl groups at both ends or a precursor thereof can
be used, for example. Moreover, the compound can be used in one
kind or in a plurality of kinds. As the compound having the
alkoxysilyl group used as the third component, a silane coupling
agent or a compound having alkoxysilyl groups at both ends is
preferred from a viewpoint of reactivity or the like.
B-1. Silane Coupling Agent
[0090] The silane coupling agent is the compound having the
alkoxysilyl group and an organic functional group in one molecule.
When the silane coupling agent is used as the third component, the
close contact of the film to the substrate can be further increased
because the organic functional group in the silane coupling agent
has affinity with polysaccharides and the derivative thereof as the
second component. Specific examples of the organic functional
groups include an amino group, a mercapto group, an epoxy group, a
vinyl group, a propenyl group and an acrylic group. Among the
groups, a compound containing an amino group or an epoxy group is
preferred from a viewpoint of a high affinity with the
polysaccharides and the derivative thereof, and a silane coupling
agent represented by the following general formula (I) or (II) is
preferred from a viewpoint of easiness of industrial procurement
and reactivity:
##STR00004##
wherein R represents alkyl group having 1 to 3 carbons, and n and m
are an integer of 2 to 5.
[0091] Furthermore, 3-aminopropyltriethoxysilane or
3-glycidoxypropyltrimethoxysilane is particularly preferred from a
viewpoint of the process resistance and the environmental
resistance.
[0092] As the compound containing the alkoxysilyl group, various
kinds of commercial products can be used. Specific examples include
Sila-Ace S210, Sila-Ace S220, Sila-Ace S310, Sila-Ace S320,
Sila-Ace S330, Sila-Ace S360, Sila-Ace S510, Sila-Ace S520,
Sila-Ace S530, Sila-Ace S710, Sila-Ace S810, Sila-Ace S340,
Sila-Ace S350 and Sila-Ace XS1003 (trade name) (JNC Corporation),
Z-6610, Z-6011, Z-6020, Z-6094, Z-6883, Z-6032, Z-6040, Z-6044,
Z-6042, Z-6043, Z-6075, Z-6300, Z-6519, Z-6825, Z-6030, Z-6033,
Z-6062, Z-6862, Z-6911, Z-6026, AZ-720 and Z-6050 (trade name) (Dow
Corning Toray Co., Ltd.).
B-2. Compound Having Alkoxysilyl Groups at Both Ends
[0093] When using the compound having alkoxysilyl groups at both
ends as the third component, a siloxane oligomer having a large
molecular weight is formed by the compounds having alkoxysilyl
groups with each other during calcination, and thus physical
strength of the film can be further increased. The compounds are
represented by the following general formula (III), for
example:
##STR00005##
wherein R represents alkyl group having 1 to 3 carbons, and n is an
integer of 2 to 5. As R, a methyl group or an ethyl group is
preferred in view of reactivity or easiness of industrial
procurement, and n is preferably 2 or 3.
[0094] From a viewpoint of environmental resistance, process
resistance and close contact of the transparent conductive film
obtained, content of the third component is preferably in the range
of approximately 1.0 part by weight or more to approximately 50
parts by weight or less, further preferably, in the range of
approximately 2.5 parts by weight or more approximately to 25 parts
by weight or less, still further preferably, in the range of
approximately 5.0 parts by weight or more to approximately 15 parts
by weight or less based on 100 parts by weight of the second
component.
[0095] An aspect of a reaction when using
3-aminopropyltriethoxysilane as the third component is shown in the
following scheme (2). In the diagram, an aspect of forming a
siloxane bond between the substrate and 3-aminopropyltrisilanol
produced by hydrolysis of 3-aminopropyltriethoxysilane and between
3-aminopropyltrisilanols is schematically shown. The present
invention is not limited to the following scheme (2):
##STR00006##
1-4. Fourth Component: Water
[0096] The coating forming composition of the present invention
contains water being the solvent as the fourth component. The
fourth component disperses the first component, dissolves the
second component and the third component, and simultaneously
evaporates during film formation, and thus a film having
conductivity is formed. From a viewpoint of controlling viscosity
or evaporation rate and dispersibility, the fourth component may
contain alcohol, ketone or ether, and a salt of lithium, sodium,
potassium, calcium, ammonium or the like, and also an acid or base
such as hydrochloric acid and ammonia.
1-5. Any Component
[0097] The coating forming composition of the present invention may
contain any component in the range where properties of the
composition are not adversely affected. Specific examples of any of
components include a binder component other than the second
component, a corrosion inhibitor, a close contact accelerator, a
surfactant, a viscosity modifier and an organic solvent.
1-5-1. Binder Component Other than the Second Component
[0098] Specific examples of binder components other than the binder
components as described in claims include a vinyl compound, such as
polyvinyl acetate, polyvinyl alcohol and polyvinyl formal, a
biopolymer compound, such as protein, gelatin and polyamino acid, a
polyacryloyl compound, such as polymethylmethacrylate, polyacrylate
and polyacrylonitrile, a polyester, such as polyethylene
terephthalate, polyester naphthalate and polycarbonate,
polystyrene, polyvinyl toluene, polyvinyl xylene, polyimide,
polyamideimide, polyether imide, polysulfide, polysulfone,
polyphenylenes, polyphenyl ether, polyurethane, epoxy
(meth)acrylate, melamine (meth)acrylate, a polyolefin such as
polypropylene, polymethylpentane, and cyclic olefin, an
acrylonitrile-butadiene-styrene copolymer (ABS), silicone resin,
polyvinyl chloride, chlorinated polyethylene, chlorinated
polypropylene, polyacetate, polynorbornene, synthetic rubber, a
fluorinated polymer such as polyfluorovinylidene,
polytetrafluoroethylene, polyhexafluoropropylene, a copolymer of
fluoroolefin-hydrocarbon olefin and fluorocarbon polymer. However,
the binder component is not limited thereto.
1-5-2. Corrosion Inhibitor
[0099] As the corrosion inhibitor, a specific nitrogen-containing
organic compound and a specific sulfur-containing organic compound
such as aromatic triazole, imidazole, thiazole and thiol, a
biomolecule showing a specific affinity to a metal surface, a
compound for blocking a corrosive element by competing with a metal
or the like is known. Moreover, metal nanowires may be protected
based on a different mechanism by a different corrosion
inhibitor.
[0100] Specific examples of the corrosion inhibitors include,
alkyl-substituted benzotriazole, such as tolyltriazole and
butylbenzyltriazole, 2-aminopyrimidine, 5,6-dimethylbenzimidazole,
2-amino-5-mercapto-1,3,4-thiadiazole, 2-mercaptopyrimidine,
2-mercaptobenzoxazole, 2-mercaptobenzothiazole,
2-mercaptobenzimidazole, cysteine, dithiothiadiazole, saturated C6
to C24 linear alkyl dithiothiadiazole, saturated C6 to C24 linear
alkylthiol, acrolein, glyoxal, triazine and n-chlorosuccinimide,
but not limited thereto. Moreover, the corrosion inhibitor may be
used in one kind or in combination of two or more kinds.
1-5-3. Surfactant
[0101] The coating forming composition of the present invention may
contain the surfactant for improving wettability to a base
substrate or uniformity of a surface of a hardened film obtained,
for example. Specific examples of the surfactants include a
silicone surfactant, an acrylic surfactant or a fluorinated
surfactant.
[0102] Specific examples of commercial products of the surfactants
include Zonyl FSO-100, Zonyl FSN, Zonyl FSO and Zonyl FSH (trade
name) (E. I. du Pont de Nemours & Co.), Triton X-100, Triton
X-114 and Triton X-45 (trade name) (Sigma-Aldrich Japan K.K.),
Dynol 604 and Dynol 607 (trade name) (Air Products Japan, Inc.),
n-Dodecyl-.beta.-D-maltoside, Novek, Byk-300, Byk-306, Byk-335,
Byk-310, Byk-341, Byk-344, Byk-370, Byk-354, Byk-358 and Byk-361
(trade name) (BYK-Chemie Japan K. K.), DFX-18, Futargent 250 and
Futargent 251 (trade name) (Neos Co., Ltd.), Megafac F-444, Megafac
F-479 and Megafac F-472SF (trade name) (DIC, Inc.). However, the
surfactant is not limited thereto. Moreover, the surfactant may be
used in one kind or in combination of two or more kinds.
1-5-3. Organic Solvent
[0103] The coating forming composition of the present invention may
contain the organic solvent for the purpose of adjusting
compatibility. Specific examples of the organic solvents include
methanol, ethanol, isopropanol, butanol or 1-methoxy-2-propanol.
However, the organic solvent is not limited thereto. Moreover, the
organic solvent may be used alone or by mixing the organic
solvents.
Composition and Physical Properties of the Coating Forming
Composition
[0104] From a viewpoint of a favorable dispersibility of each
component in the composition, and a high conductivity, a favorable
optical transparency, a favorable environmental resistance, a
favorable process resistance and a favorable close contact of the
coating obtained from the composition of the present invention,
content of each component in the coating forming composition of the
present invention is preferably in the range of approximately 0.01%
by weight or more to approximately 1.0% by weight or less for the
first component based on the total weight of the coating forming
composition, in the range of approximately 50 parts by weight or
more to approximately 300 parts by weight or less for the second
component based on 100 parts by weight of the first component and
in the range of approximately 1.0 part by weight or more to
approximately 50 parts by weight or less for the third component
based on 100 parts by weight of the second component, further
preferably, in the range of approximately 0.05% by weight or more
to approximately 0.75% by weight or less for the first component
based on the total weight of the coating forming composition, in
the range of approximately 75 parts by weight or more to
approximately 250 parts by weight or less for the second component
based on 100 parts by weight of the first component and in the
range of approximately 2.5 parts by weight or more to approximately
25 parts by weight or less for the third component based on 100
parts by weight of the second component, still further preferably,
in the range of approximately 0.1% by weight or more to
approximately 0.5% by weight or less for the first component based
on the total weight of the coating forming composition, in the
range of approximately 100 parts by weight or more to approximately
200 parts by weight or less for the second component based on 100
parts by weight of the first component and in the range of
approximately 5.0 parts by weight or more to approximately 15 parts
by weight or less for the third component based on 100 parts by
weight of the second component.
[0105] More specifically, based on the total amount of the first
component to the fourth component, the composition of each
component is preferably in the range of approximately 0.01% by
weight or more to approximately 1.0% by weight or less for the
first component, in the range of approximately 0.005% by weight or
more to approximately 3.0% by weight or less for the second
component, in the range of approximately 0.00005% by weight or more
to approximately 1.5% by weight or less for the third component and
in the range of approximately 94.5% by weight or more to
approximately 99.9395% by weight or less for the fourth component,
further preferably, in the range of approximately 0.05% by weight
or more to approximately 0.75% by weight or less for the first
component, in the range of approximately 0.0375% by weight or more
to approximately 1.875% by weight or less for the second component,
in the range of approximately 0.0009375% by weight or more to
approximately 0.46875% by weight or less for the third component
and in the range of approximately 96.90625% by weight or more to
approximately 99.9115625% by weight or less for the fourth
component, still further preferably, in the range of approximately
0.1% by weight or more to approximately 0.5% by weight or less for
the first component, in the range of approximately 0.1% by weight
or more to approximately 1.0% by weight or less for the second
component, in the range of approximately 0.005% by weight or more
to approximately 0.15% by weight or less for the third component
and in the range of approximately 98.35% by weight or more to
approximately 99.795% by weight or less for the fourth
component.
[0106] The coating forming composition of the present invention can
be manufactured by appropriately selecting agitating, mixing,
heating, cooling, dissolving, dispersing or the like of the
components as described above according to a known method.
[0107] As a viscosity of the coating forming composition of the
present invention is higher, precipitation of the metal nanowires
and the metal nanotubes is suppressed, and a more uniform
dispersibility is obtained for a long period of time. Moreover, as
the viscosity is higher, a film having a higher conductivity can be
obtained because film thickness can be increased under fixed
application conditions. On the other hand, as the viscosity is
lower, smoothness and uniformity of the coating is better. Thus,
the viscosity at 25.degree. C. of the coating forming composition
of the present invention is preferably in the range of
approximately 1 mPas or more to approximately 100 mPas or less,
further preferably, in the range of approximately 10 mPas or more
to approximately 70 mPas or less. In the present invention, the
viscosity is a value measured by using a cone plate type rotational
viscometer.
Method for Manufacturing a Substrate Having a Transparent
Conductive Film
[0108] The substrate having the transparent conductive film can be
manufactured by using the coating forming composition of the
present invention. The method for manufacturing the substrate
includes a process for forming the coating on the substrate by
applying the composition on the substrate, and then heating the
substrate at temperature in the range of approximately 30.degree.
C. or higher to 80.degree. C. or lower, and subsequently
calcinating the substrate at temperature in the range of
approximately 120.degree. C. or higher to 240.degree. C. or
lower.
[0109] The coating having the conductivity, the environmental
resistance and the process resistance is formed on the substrate by
applying the composition onto the substrate, and then removing the
solvent.
[0110] As the substrate, properties may be rigid or flexible or
colored. Specific examples of the materials of the substrate
include glass, polyimide, polycarbonate, polyethersulfone,
acryloyl, polyester, polyethylene terephthalate, polyethylene
naphthalate, polyolefin and polyvinyl chloride. The materials
preferably have a high light transmittance and a low haze value.
Furthermore, a circuit such as a TFT element may be preferably
formed on the substrate or an organic functional material such as a
color filter and an overcoat, or an inorganic functional material
such as a silicon nitride or silicon oxide film may be formed
thereon. Moreover, a number of the substrates may be laminated.
[0111] As a method for applying the composition of the present
invention to the substrate, a general method such as a spin coating
method, a slit coating method, a dip coating method, a blade
coating method, a spray method, a relief printing method, an
intaglio printing method, a planographic printing method, a
dispensing method and an ink jet method can be used. From a
viewpoint of the uniformity of the film thickness and productivity,
the spin coating method and the slit coating method are preferred,
and the slit coating method is further preferred.
[0112] Surface resistance is determined depending on an
application.
[0113] The surface resistance is determined depending on the film
thickness and surface density of the first component. The film
thickness and the surface density of the first component are
determined depending on viscosity and a concentration of the first
component in the coating forming composition. The film thickness is
determined depending on application conditions. Accordingly, a
desired surface resistance is controlled by the viscosity and the
concentration of the first component in the coating forming
composition.
[0114] A larger film thickness is better from a viewpoint of a low
surface resistance, and a smaller film thickness is better from a
viewpoint of suppressing occurrence of a poor display due to a
step. Therefore, when comprehensively taking the facts into
consideration, the film thickness is preferably in the range of
approximately 5 nanometers to approximately 500 nanometers, further
preferably, in the range of approximately 5 nanometers to
approximately 200 nanometers, still further preferably, in the
range of approximately 5 nanometers to approximately 100
nanometers.
[0115] The solvent is removed by performing heating treatment of an
applied article when necessary. As heating temperature, heating is
ordinarily performed at temperature in the range of approximately
30.degree. C. to approximately a boiling point of the solvent plus
50.degree. C., although the range is different depending on kinds
of solvents.
[0116] The surface resistance and the total transmittance of the
film obtained can be adjusted to a desired value by adjusting the
film thickness or an applied amount of the composition, conditions
of the method of application, and the concentration of the first
component in the coating forming composition of the present
invention.
[0117] In general, as the film thickness is larger, the surface
resistance and the total transmittance are decreased. Moreover, as
the concentration of the first component in the coating forming
composition is higher, the surface resistance and the total
transmittance are decreased.
[0118] The coating obtained as described above has preferably a
surface resistance in the range of approximately 1
.OMEGA./.quadrature. or more to approximately 10,000
.OMEGA./.quadrature. or less and a total transmittance of
approximately 80% or more, further preferably, a surface resistance
in the range of approximately 10 .OMEGA./.quadrature. or more to
approximately 5,000 .OMEGA./.quadrature. or less and a total
transmittance of approximately 85% or more.
[0119] In the present invention, the surface resistance refers to a
measured value according to a noncontact measurement method as
described later, unless otherwise noted.
Patterning of a Transparent Conductive Film
[0120] Patterning of the transparent conductive film prepared
according to the present invention can be performed according to
the application. As the method, a photolithographic method using a
resist material generally used for patterning of ITO can be
applied. Procedures of the photolithographic method are shown
below.
(1) Resist application
(2) Calcination
(3) Exposure
(4) Development
(5) Etching
(6) Peeling
Any Process
[0121] Before and after each process of film formation and
patterning of the composition described above, a suitable treatment
process, a suitable cleaning process and a suitable drying process
may be appropriately applied. Specific examples of the treatment
processes include a plasma surface treatment, an ultrasonic
treatment, an ozone treatment and a cleaning process using a
suitable solvent and a heat treatment. Moreover, a process for
immersing into water may be applied. Thus, immersing into water is
preferred from a viewpoint of a low surface resistance.
[0122] The plasma surface treatment can be applied for improving
applicability of the coating forming composition or a developer.
For example, the surface of the substrate or the coating forming
composition on the substrate can be treated under conditions of 100
W, 90 seconds, an oxygen flow rate of 50 sccm (sccm; standard
cc/min) and a pressure of 50 Pa by using oxygen plasma. According
to the ultrasonic treatment, particulates physically deposited or
the like on the substrate can be removed by immersing the substrate
into a solution, and propagating an ultrasonic wave about 200 kHz,
for example. According to the ozone treatment, a deposit or the
like on the substrate can be effectively removed by blowing air to
the substrate and simultaneously irradiating the substrate with an
ultraviolet light and utilizing oxidizing power of ozone generated
by the ultraviolet light. According to the cleaning treatment, a
particulate impurity can be washed out and removed by spraying pure
water in a mist form or a shower form and utilizing dissolving
capability and pressure of the pure water, for example. The heat
treatment is a method for removing a compound to be desirably
removed in the substrate by volatilizing the compound. Heating
temperature is appropriately set up in consideration of a boiling
point of the compound to be desirably removed. For example, when
the compound to be desirably removed is water, the substrate is
heated at temperature in the range of approximately 50.degree. C.
to about 80.degree. C.
[0123] The surface resistance and the total transmittance of the
transparent conductive film on the substrate having a transparent
conductive film subjected to patterning as obtained according to
the manufacturing method as described above has preferably a
surface resistance in the range of approximately 1
.OMEGA./.quadrature. or more to approximately 10,000
.OMEGA./.quadrature. or less and a total transmittance of
approximately 80% or more, further preferably, a surface resistance
in the range of approximately 10 .OMEGA./.quadrature. or more to
approximately 5,000 .OMEGA./.quadrature. or less and a total
transmittance of approximately 85% or more.
[0124] Herein, "total transmittance" is a ratio of transmitted
light to an incident light, and the transmitted light includes a
directly transmitted component and a scattered component. A light
source is illuminant C and a spectrum is a CIE luminosity function
y. Moreover, the film thickness is preferably in the range of
approximately 5 nanometers or more to approximately 100 nanometers
or less, further preferably, in the range of approximately 10
nanometers or more to approximately 80 nanometers or less, still
further preferably, in the range of approximately 20 nanometers or
more to approximately 80 nanometers or less, although the film
thickness is different according to the application.
[0125] Such surface resistance and total transmittance can be
adjusted to a desired value by adjusting the film thickness or an
applied amount of the composition, and conditions of the method of
application, and the concentration of the first component in the
coating forming composition of the present invention.
[0126] As for the transparent conductive film subjected to
patterning, an insulating film, an overcoat having a protective
function or a polyimide layer having an orientation function can be
further arranged on the surface thereof.
Application of the Substrate Having the Transparent Conductive Film
Subjected to Patterning
[0127] The substrate having the transparent conductive film
subjected to patterning is used for a device element from
conductivity and optical properties thereof.
[0128] Specific examples of the device elements include a liquid
crystal display element, an organic electroluminescence element, an
electronic paper, a touch panel element and a photovoltaic cell
element.
[0129] The device element may be prepared by using a rigid
substrate or a flexible substrate or the combination thereof.
Moreover, the substrate used for the device element may be
transparent or colored.
[0130] Specific examples of the transparent conductive films used
for the liquid crystal display element include a picture element
electrode to be formed on a side of a thin film transistor (TFT)
array substrate and a common electrode formed on a side of a color
filter substrate. Specific examples of display modes of LCD include
Twisted Nematic (TN), Multi Vertical Alignment (MVA), Patterned
Vertical Alignment (PVA), In Plane Switching (IPS), Fringe Field
Switching (FFS), Polymer Stabilized Vertical Alignment (PSA),
Optically Compensated Bend (OCB), Continuous Pinwheel Alignment
(CPA) and Blue Phase (BP). Moreover, a transmissive type, a
reflective type and a transreflecive type are provided for each of
the modes. The picture element electrode of LCD is subjected to
patterning for each picture element, and is electrically connected
to a drain electrode of TFT. In addition, the IPS mode has a comb
electrode structure, and the PVA mode has structure in which slits
are curved in the picture element, for example.
[0131] The transparent conductive film used for the organic
electroluminescence element is ordinarily subjected to patterning
in a stripe on the substrate, when the film is used as a conductive
region of a passive type driving mode. A direct current voltage is
applied between the conductive region in the stripe (anode) and a
conductive region in a stripe arranged orthogonally thereto
(cathode), and thus display is conducted by allowing picture
elements in the matrix to emit light. When the film is used as an
electrode of an active type driving mode, the film is subjected to
patterning on the side of the TFT array substrate for each picture
element.
[0132] The touch panel element includes a resistive type and a
capacitive type depending on the detection method, and a
transparent electrode is used for any of the types. The transparent
electrode used for the capacitive type is subjected to
patterning.
[0133] The electronic paper includes a microcapsule type, a quick
response liquid powder type, a liquid crystal type, an
electrowetting type, an electrophoretic type and a chemical
reaction change type depending on the display method, and the
transparent electrode is used for any of the types. The transparent
electrode is subjected to patterning into any shape,
respectively.
[0134] The photovoltaic cell element includes a silicon type, a
compound type, an organic type and a quantum dot type depending on
a material of an optical absorption layer, and the transparent
electrode is used for any of the types. The transparent electrode
is subjected to patterning in any shape, respectively.
[0135] It will be apparent to those skilled in the art that various
modifications and variations can be made in the invention and
specific examples provided herein without departing from the spirit
or scope of the invention. Thus, it is intended that the invention
covers the modifications and variations of this invention that come
within the scope of any claims and their equivalents.
[0136] The following examples are for illustrative purposes only
and are not intended, nor should they be interpreted to, limit the
scope of the invention.
EXAMPLES
[0137] In the following, the present invention will be further
specifically explained based on Examples, but the present invention
is not limited to the Examples. In Examples and Comparative
Examples, ultrapure water was used as water being a constituent.
However, ultrapure water may be referred to simply as water in the
following. Preparation was performed using Puric FPC-0500-0M0
(trade name) (Organo Corporation) as ultrapure water.
[0138] Measurement methods or evaluation methods in each evaluation
item were applied according to the following methods.
[0139] Unless otherwise noted, measurements (1) to (4) were carried
out in a region in which a transparent conductive film of a sample
to be evaluated is formed.
(1) Measurement of Surface Resistance
[0140] As the evaluation method, two kinds of a four-point probe
method and a noncontact measurement method were applied.
[0141] Loresta-GPMCP-T610 (Mitsubishi Chemical Corporation) was
used for the four-point probe measurement method (in accordance
with JIS K7194). A probe used for measurement is a proprietary ESP
type probe having a distance of 5 millimeters between pins, and a
pin point diameter of 2 millimeters. Surface resistance
(.OMEGA./.quadrature.) was calculated by bringing the probe into
contact with the sample to be evaluated, measuring a potential
difference between inside two terminals when applying a fixed
current to outside two terminals, and multiplying resistance
obtained by the measurement by a correction coefficient. Volume
resistivity (Qcm) and conductivity (Siemens/cm) can be determined
from the thus obtained surface resistance value and thickness of a
conductive film.
[0142] According to the four-point probe measurement method,
surface resistance of the conductive film on the substrate in which
at least one insulating film was formed on the conductive film, and
surface resistance of the conductive film in which metal nanowires
or metal nanotubes as shown in the specification were dispersed
into an insulator cannot be stably measured sometimes. In the case,
a noncontact surface resistance measurement method using an eddy
current was applied. As the noncontact measurement method, surface
resistance (.OMEGA./.quadrature.) was measured using 717 B-H
(DELCOM). Also in the case, volume resistivity (Qcm) and
conductivity (Siemens/cm) can be determined from the thus obtained
surface resistance value and thickness of the conductive film. In
addition, a measured value according to the four-point probe method
and a measured value according to the noncontact measurement method
agree substantially. The noncontact measurement method was used,
unless otherwise noted.
(2) Measurement of Total Transmittance and Haze
[0143] Haze-gard plus (BYK Gardner, Inc.) was used for measurement
of total transmittance and haze. Air was used as a reference.
(3) Film Thickness
[0144] Profilometer P-16+ (KLA-Tencor) was used for measurement of
film thickness.
[0145] The film thickness was measured in accordance with "Test
method for thickness of fine ceramic thin films--Film thickness by
contact probe profilometer" (JIS R1636). When measuring film
thickness of a film not subjected to patterning, a part of films of
a sample to be evaluated was shaved off, and a profile on a
boundary surface was measured.
(4) Testing of Environmental Resistance
[0146] Environmental resistance was evaluated by leaving a
transparent conductive film to stand in a constant temperature oven
at 70.degree. C., and a high temperature and high humidity oven at
70.degree. C. and 90% RH, measuring total transmittance and haze
after 500 hours, and comparing a measured value with an initial
value.
[0147] When comparing the surface resistance and the total
transmittance and the haze with the initial value in terms of a
rate of change, evaluation results were determined to be good when
the rate of change of all of the properties are in the range of 0%
or more to 50% or less, marginal when the rate of change of at
least one of the properties is in the range of 51% or more to 100%
or less, and bad when the rate of change of at least one of the
properties is in the range of 101% or more.
(5) Testing of Process Resistance
[0148] Water was sprayed to a sample to be evaluated at a pressure
of 270 kPa for 1 or 5 minutes by using Developer EX-25D (Yoshitani
Shokai K. K). Process resistance was evaluated by performing (a)
visual inspection of presence or absence of film peeling, (b)
measurement of surface resistance, and (c) measurement of total
transmittance and haze before and after spraying.
[0149] The film was visually observed, and evaluation results were
determined to be good when no peeling of the film was observed
under conditions of 270 kPa for 1 minute, marginal when peeling was
observed in an area of 1% or more to less than 50% of the
substrate, and bad when peeling was observed in an area of 50% or
more to 100% or less of the substrate. A sample determined to be
good according to the evaluation results was evaluated under
conditions of 270 kPa for 5 minutes, and when no peeling of the
film was observed, the sample was determined to be excellent.
(6) Measurement of Viscosity of a Composition
[0150] As for a viscosity of a composition used in Examples,
viscosity when temperature was 25.degree. C. and a shear rate was
100 s.sup.-1 was measured using TV-22 viscometer (Toki Sangyo Co.,
Ltd.).
(7) Testing of Dispersion Stability of a Composition
(Dispersibility)
[0151] After putting 10 g of a composition used in Examples in a
screw vial of 20 mL and sufficiently shaking the vial up, the vial
was left to stand for one week under room temperature.
Precipitation of silver nanowires after leaving the vial to stand
was visually confirmed. A composition where no precipitation of
silver nanowires was observed was determined to be good, a
composition where contrasting density was observed to be marginal,
and a composition where precipitation of silver nanowires was
observed in the bottom of the screw vial to be bad.
(8) Testing of Close Contact
[0152] A cross cut test was performed using 3M396 tape (trade name)
(Sumitomo 3M Co., Ltd.), and the number of residues after tape
peeling in 100 cross cuts having a size of 1 mm.times.1 mm was
evaluated. A tape where no peeling was observed was determined to
be good, a tape where peels of 1 or more to less than 50 were
observed to be marginal, and a tape where peels of 50 or more to
100 or less were observed to be bad.
[0153] The first component (metal nanowires or metal nanotubes)
used in the present invention was prepared as described below.
Preparation of Silver Nanowires
[0154] A reaction mixture containing silver nanowires was obtained
by putting 4.171 g of poly(N-vinylpyrrolidone) (trade name;
Polyvinylpyrrolidone K30, MW 40,000, Tokyo Kasei Kogyo Co., Ltd.),
70 mg of tetrabuthylammonium chloride (trade name;
Tetrabuthylammonium chloride, Wako Pure Chemical Industries, Ltd.),
4.254 g of silver nitrate (trade name; Silver nitrate, Wako Pure
Chemical Industries, Ltd.) and 500 mL of ethylene glycol (trade
name; Ethylene glycol, Wako Pure Chemical Industries, Ltd.) in a
1,000 mL flask, agitating the mixture for 15 minutes and uniformly
dissolving the mixture, and agitating the mixture at 110.degree. C.
for 16 hours in an oil bath.
[0155] Subsequently, the reaction mixture was returned to room
temperature (25 to 30.degree. C.), and then a reaction solvent was
replaced to water with a centrifuge (As One Corporation), and thus
aqueous silver nanowires dispersion solution I having any
concentration was obtained. According to the operation, unreacted
silver nitrate, poly(N-vinylpyrrolidone) used as a mold,
tetrabuthylammonium chloride, ethylene glycol and silver
nanoparticles having a small particle size in the reaction mixture
were removed. An aqueous silver nanowires dispersion solution
having any concentration was obtained by redispersing precipitates
on a filter paper into water. Mean values of a minor axis, a major
axis and an aspect ratio of the silver nanowires were 68
nanometers, 18 micrometers and 265, respectively.
[0156] A binder solution being the second component
(polysaccharides and the derivative thereof) used in the present
invention was prepared as described below.
Preparation of Binder Solution I
[0157] In a 300 mL beaker whose tare weight was premeasured, 100 g
of ultrapure water was put, and heated and agitated. At a liquid
temperature of 80 to 90.degree. C., 2.00 g of hydroxypropyl methyl
cellulose (abbreviated as HPMC, trade name; Metolose 60SH-10000,
Shin-Etsu Chemical Co., Ltd., 10,000 mPas in viscosity of a 2 wt. %
aqueous solution) was put in the beaker little by little, and
agitated strongly to disperse HPMC uniformly. While keeping strong
agitation, 80 g of ultrapure water was added, and simultaneously
heating was stopped, and agitation was continued while cooling the
beaker with ice water until a uniform solution was formed. After
agitation for 20 minutes, ultrapure water was added for weight of
an aqueous solution to be 200.00 g, and agitation was continued for
further 10 minutes at room temperature until a uniform solution was
formed, and thus 1 wt. % aqueous HPMC solution I was prepared.
[0158] Then 0.8 wt. % binder solution I was prepared by measuring
32.00 g of 1 wt. % HPMC solution I, 3.20 g of 0.1 wt. % aqueous
TritonX-100 (trade name) (Sigma-Aldrich Japan, Inc.) solution and
4.80 g of ultrapure water, and agitating the mixture until a
uniform solution was formed.
Preparation of Binder Solution II
[0159] Then 0.8 wt. % binder solution II was prepared in a manner
similar to preparation of binder solution I except that
hydroxypropyl methyl cellulose was changed to a large molecular
weight product (trade name; Metolose 90SH-100000, Shin-Etsu
Chemical Co., Ltd., 100,000 mPas in viscosity of a 2 wt. % aqueous
solution).
Preparation of Binder Solution III
[0160] Then 0.8 wt. % binder solution III was prepared by
performing operation in a manner similar to preparation of binder
solution I except that hydroxypropyl methyl cellulose was changed
to a smaller molecular weight product (trade name;
(Hydroxypropyl)methyl cellulose, Aldrich Corporation, 4,000 mPas in
viscosity of a 2 wt. % aqueous solution).
Preparation of Binder Solution IV
[0161] Then 0.8 wt. % binder solution IV was prepared by performing
operation in a manner similar to preparation of binder solution I
except that hydroxypropyl methyl cellulose was changed to a larger
molecular weight product (trade name; Metolose SHV-PF, 200,000 mPas
in viscosity of a 2 wt. % aqueous solution).
Example 1
Preparation of Aqueous Polymer Solution I (Third Component)
[0162] Then 1.0 wt. % aqueous polymer solution I was prepared by
measuring 0.10 g of Riken Resin MM-35 (trade name; Methylol
Melamine Resin, Miki Riken Industrial Co., Ltd.) having a solids
concentration of 80% by weight and 22.9 mg of Riken Fixer RC-3
(trade name) (catalyst, Miki Riken Industrial Co., Ltd.) having a
solids concentration of 35% by weight, and diluting the mixture
with 7.88 g of ultrapure water.
Preparation of a Coating Forming Composition
[0163] Then 4.00 g of 0.8 wt. % binder solution I, 1.60 g of 1.0
wt. % aqueous silver nanowires dispersion solution I and 2.08 g of
ultrapure water were measured and agitated until a uniform solution
was formed. Subsequently, 0.32 g of aqueous polymer solution I
having a solid content of 1.0% by weight was added and agitated
until a uniform solution was formed, and thus a coating forming
composition having the following composition was obtained. The
prepared coating forming composition had a viscosity of 15 mPas,
and showed a favorable dispersibility.
TABLE-US-00001 Silver nanowires 0.2 % by weight HPMC 0.4 % by
weight Riken Resin MM-35 0.04 % by weight Riken Fixer RC-3 0.004 %
by weight Triton X-100 0.004 % by weight Water 99.352 % by
weight
In addition, HPMC corresponded to 200 parts by weight based on 100
parts by weight of silver nanowires, Riken Resin MM-35 corresponded
to 10 parts by weight based on 100 parts by weight of HPMC, and
Riken Fixer RC-3 corresponded to 10 parts by weight based on 100
parts by weight of Riken Resin MM-35.
Preparation of a Transparent Conductive Film
[0164] On a surface of 0.7 mm-thick Eagle XG (trade name) (Corning,
Inc.) glass substrate subjected to UV ozone treatment with being
irradiated at an irradiation energy of 1,000 mJ/cm.sup.2 (low
pressure mercury lamp (254 nanometers)), 1 mL of the coating
forming composition obtained was dropped, and spin coating was
performed at 800 rpm using a spin coater (trade name; MS-A150,
Mikasa Inc.). Preliminary calcination was performed on the glass
substrate on a hot stage at 50.degree. C. under conditions for 90
seconds, and then major calcination was performed for 3 minutes on
a hot stage at 140.degree. C., and thus a transparent conductive
film was prepared.
Evaluation of the Transparent Conductive Film
[0165] The transparent conductive film obtained had a surface
resistance value of 47.4 .OMEGA./.quadrature., a total
transmittance of 91.4%, a haze of 1.6% and a film thickness of 35
nanometers. Moreover, environmental resistance, process resistance
and close contact were favorable. Furthermore, the environmental
resistance, the process resistance and the close contact were
favorable also on silicon nitride and an overcoat (product name;
PIG-7424, JNC Corporation).
[0166] The evaluation results were shown in Table 1. In addition,
only an evaluation using a glass was summarized in the table.
Example 2
[0167] A coating forming composition having the following
composition was prepared according to procedures similar to Example
1 except that an amount of 1.0 wt. % aqueous Riken Resin MM-35
solution was changed to 0.080 g. The prepared coating forming
composition showed favorable dispersibility.
TABLE-US-00002 Silver nanowires 0.2 % by weight HPMC 0.4 % by
weight Riken Resin MM-35 0.01 % by weight Riken Fixer RC-3 0.001 %
by weight Triton X-100 0.004 % by weight Water 99.385 % by
weight
In addition, HPMC corresponded to 200 parts by weight based on 100
parts by weight of silver nanowires, Riken Resin MM-35 corresponded
to 2.5 parts by weight based on 100 parts by weight of HPMC, and
Riken Fixer RC-3 corresponded to 10 parts by weight based on 100
parts by weight of Riken Resin MM-35.
[0168] A transparent conductive film was prepared according to
procedures similar to Example 1. The transparent conductive film
obtained had a surface resistance value of 43.9
.OMEGA./.quadrature., a total transmittance of 91.3% and a haze of
1.6%. Moreover, environmental resistance and process resistance
were favorable.
Example 3
[0169] A coating forming composition having the following
composition was prepared according to procedures similar to Example
1 except that an amount of 1.0 wt. % aqueous Riken Resin MM-35
solution was changed to 1.28 g. The prepared coating forming
composition showed favorable dispersibility.
TABLE-US-00003 Silver nanowires 0.2 % by weight HPMC 0.4 % by
weight Riken Resin MM-35 0.16 % by weight Riken Fixer RC-3 0.016 %
by weight Triton X-100 0.004 % by weight Water 99.220 % by
weight
In addition, HPMC corresponded to 200 parts by weight based on 100
parts by weight of silver nanowires, Riken Resin MM-35 corresponded
to 40 parts by weight based on 100 parts by weight of HPMC, and
Riken Fixer RC-3 corresponded to 10 parts by weight based on 100
parts by weight of Riken Resin MM-35.
[0170] A transparent conductive film was prepared according to
procedures similar to Example 1 except that spin coating was
performed at 500 rpm. The transparent conductive film obtained had
a surface resistance value of 103 .OMEGA./.quadrature., a total
transmittance of 89.3% and a haze of 2.3%. Moreover, environmental
resistance and process resistance were favorable.
Example 4
[0171] A coating forming composition having the following
composition was prepared according to procedures similar to Example
1 except that a binder solution used was changed to 4.00 g of 0.8
wt. % binder solution II. The prepared coating forming composition
showed favorable dispersibility.
TABLE-US-00004 Silver nanowires 0.2 % by weight HPMC 0.4 % by
weight Riken Resin MM-35 0.04 % by weight Riken Fixer RC-3 0.004 %
by weight Triton X-100 0.004 % by weight Water 99.352 % by
weight
In addition, HPMC corresponded to 200 parts by weight based on 100
parts by weight of silver nanowires, Riken Resin MM-35 corresponded
to 10 parts by weight based on 100 parts by weight of HPMC, and
Riken Fixer RC-3 corresponded to 10 parts by weight based on 100
parts by weight of Riken Resin MM-35.
[0172] A transparent conductive film was prepared according to
procedures similar to Example 1 except that spin coating was
performed at 1,000 rpm. The transparent conductive film obtained
had a surface resistance value of 30.8 .OMEGA./.quadrature., a
total transmittance of 91.2% and a haze of 1.7%. Moreover,
environmental resistance and process resistance were favorable.
Example 5
[0173] A coating forming composition having the following
composition was prepared according to procedures similar to Example
4 except that 3.20 g of 0.1 wt. % Futargent 251 (trade name) (Neos
Co., Ltd.) was used in place of 3.20 g of 0.1 wt. % aqueous Triton
X-100 solution. The prepared coating forming composition showed
favorable dispersibility.
TABLE-US-00005 Silver nanowires 0.2 % by weight HPMC 0.4 % by
weight Riken Resin MM-35 0.04 % by weight Riken Fixer RC-3 0.004 %
by weight Futargent 251 0.004 % by weight Water 99.352 % by
weight
In addition, HPMC corresponded to 200 parts by weight based on 100
parts by weight of silver nanowires, Riken Resin MM-35 corresponded
to 10 parts by weight based on 100 parts by weight of HPMC, and
Riken Fixer RC-3 corresponded to 10 parts by weight based on 100
parts by weight of Riken Resin MM-35.
[0174] A transparent conductive film was prepared according to
procedures similar to Example 4. The transparent conductive film
obtained had a surface resistance value of 29.8
.OMEGA./.quadrature., a total transmittance of 91.2% and a haze of
1.8%. Moreover, environmental resistance and process resistance
were favorable.
Example 6
[0175] A coating forming composition having the following
composition was prepared according to procedures similar to Example
1 except that a binder solution used was changed to 4.00 g of 0.8
wt. % binder solution III. The prepared coating forming composition
showed favorable dispersibility.
TABLE-US-00006 Silver nanowires 0.2 % by weight HPMC 0.4 % by
weight Riken Resin MM-35 0.04 % by weight Riken Fixer RC-3 0.004 %
by weight Triton X-100 0.004 % by weight Water 99.352 % by
weight
In addition, HPMC corresponded to 200 parts by weight based on 100
parts by weight of silver nanowires, Riken Resin MM-35 corresponded
to 10 parts by weight based on 100 parts by weight of HPMC, and
Riken Fixer RC-3 corresponded to 10 parts by weight based on 100
parts by weight of Riken Resin MM-35.
[0176] A transparent conductive film was prepared according to
procedures similar to Example 1 except that spin coating was
performed at 800 rpm. The transparent conductive film obtained had
a surface resistance value of 60.3.OMEGA./.quadrature., a total
transmittance of 92.0% and a haze of 1.3%. Moreover, environmental
resistance and process resistance were favorable.
Example 7
[0177] A coating forming composition having the following
composition was prepared according to a composition and procedures
similar to Example 1 except that a binder solution used was changed
to 4.00 g of 0.8 wt. % binder solution IV. The prepared coating
forming composition showed favorable dispersibility.
TABLE-US-00007 Silver nanowires 0.2 % by weight HPMC 0.4 % by
weight Riken Resin MM-35 0.04 % by weight Riken Fixer RC-3 0.004 %
by weight Triton X-100 0.004 % by weight Water 99.352 % by
weight
In addition, HPMC corresponded to 200 parts by weight based on 100
parts by weight of silver nanowires, Riken Resin MM-35 corresponded
to 10 parts by weight based on 100 parts by weight of HPMC, and
Riken Fixer RC-3 corresponded to 10 parts by weight based on 100
parts by weight of Riken Resin MM-35.
[0178] A transparent conductive film was prepared according to
procedures similar to Example 1 except that spin coating was
performed at 2,000 rpm. The transparent conductive film obtained
had a surface resistance value of 33.8 .OMEGA./.quadrature., a
total transmittance of 91.8% and a haze of 1.3%. Moreover,
environmental resistance and process resistance were favorable.
Example 8
Preparation of Aqueous Polymer Solution VI (Third Component)
[0179] Thus, 1.0 wt. % aqueous polymer solution VI was prepared by
measuring 0.10 g of Riken Resin MA-156 (trade name) (methylol
melamine resin, Miki Riken Industrial Co., Ltd.) having a solids
concentration of 80% and 25.8 mg of Riken Fixer RC (trade name)
(catalyst, Miki Riken Industrial Co., Ltd.) having a solids
concentration of 31%, and diluting the mixture with 7.87 g of
ultrapure water.
Preparation of a Coating Forming Composition
[0180] A coating forming composition having the following
composition was prepared according to procedures similar to Example
1 except that 1.0 wt. % aqueous polymer solution VI was used as an
aqueous polymer solution. The prepared coating forming composition
showed favorable dispersibility.
TABLE-US-00008 Silver nanowires 0.2 % by weight HPMC 0.4 % by
weight Riken Resin MA-156 0.04 % by weight Riken Fixer RC 0.004 %
by weight Triton X-100 0.004 % by weight Water 99.352 % by
weight
In addition, HPMC corresponded to 200 parts by weight based on 100
parts by weight of silver nanowires, Riken Resin MA-156
corresponded to 10 parts by weight based on 100 parts by weight of
HPMC, and Riken Fixer RC corresponded to 10 parts by weight based
on 100 parts by weight of Riken Resin MA-156.
[0181] A transparent conductive film was prepared according to
procedures similar to Example 1. The transparent conductive film
obtained had a surface resistance value of 51.1
.OMEGA./.quadrature., a total transmittance of 91.3% and a haze of
1.6%. Moreover, environmental resistance and process resistance
were favorable.
Example 9
Preparation of Aqueous Polymer Solution VII (Third Component)
[0182] Then, 1.0 wt. % aqueous polymer solution VII was prepared by
measuring 0.10 g of Riken Resin MM-35 having a solids concentration
of 80 wt. % and 25.8 mg of Riken Fixer RC (trade name) (Miki Riken
Industrial Co., Ltd.) having a solids concentration of 31 wt. %,
and diluting the mixture with 7.87 g of ultrapure water.
Preparation of a Coating Forming Composition
[0183] A coating forming composition having the following
composition was prepared according to procedures similar to Example
1 except that 1.0 wt. % aqueous polymer solution VII was used as an
aqueous polymer solution. The prepared coating forming composition
showed favorable dispersibility.
TABLE-US-00009 Silver nanowires 0.2 % by weight HPMC 0.4 % by
weight Riken Resin MM-35 0.04 % by weight Riken Fixer RC 0.004 % by
weight Triton X-100 0.004 % by weight Water 99.352 % by weight
In addition, HPMC corresponded to 200 parts by weight based on 100
parts by weight of silver nanowires, Riken Resin MM-35 corresponded
to 10 parts by weight based on 100 parts by weight of HPMC, and
Riken Fixer RC corresponded to 10 parts by weight based on 100
parts by weight of Riken Resin MM-35.
[0184] A transparent conductive film was prepared according to
procedures similar to Example 1. The transparent conductive film
obtained had a surface resistance value of 52.8
.OMEGA./.quadrature., a total transmittance of 91.2% and a haze of
1.5%. Moreover, environmental resistance and process resistance
were favorable.
Example 10
Preparation of Aqueous Polymer Solution VIII (Third Component)
[0185] Then, 1.0 wt. % aqueous polymer solution VIII was prepared
by measuring 0.10 g of Riken Resin MA-156 having a solids
concentration of 80 wt. % and 22.9 mg of Riken Fixer RC-3 having a
solids concentration of 35 wt. %, and diluting the mixture with
7.87 g of ultrapure water.
Preparation of a Coating Forming Composition
[0186] A coating forming composition having the following
composition was prepared according to procedures similar to Example
1 except that 1.0 wt. % aqueous polymer solution VIII was used as
an aqueous polymer solution. The prepared coating forming
composition showed favorable dispersibility.
TABLE-US-00010 Silver nanowires 0.2 % by weight HPMC 0.4 % by
weight Riken Resin MA-156 0.04 % by weight Riken Fixer RC-3 0.004 %
by weight Triton X-100 0.004 % by weight Water 99.352 % by
weight
In addition, HPMC corresponded to 200 parts by weight based on 100
parts by weight of silver nanowires, Riken Resin MA-156
corresponded to 10 parts by weight based on 100 parts by weight of
HPMC, and Riken Fixer RC-3 corresponded to 10 parts by weight based
on 100 parts by weight of Riken Resin MA-156.
[0187] A transparent conductive film was prepared according to
procedures similar to Example 1. The transparent conductive film
obtained had a surface resistance value of 54.0
.OMEGA./.quadrature., a total transmittance of 91.4% and a haze of
1.5%. Moreover, environmental resistance and process resistance
were favorable.
Example 11
Preparation of Aqueous Polymer Solution IX
[0188] Then, 1.0 wt. % aqueous polymer solution IX was prepared by
measuring 0.264 g of Sumirez 633 (trade name) (having an epoxy
group, Taoka Chemical Co., Ltd.) having a solids concentration of
30% by weight and diluting the mixture with 7.75 g of ultrapure
water.
Preparation of a Coating Forming Composition
[0189] A coating forming composition having the following
composition was prepared according to procedures similar to Example
1 except that 1.0 wt. % aqueous polymer solution IX was used as an
aqueous polymer solution. The prepared coating forming composition
showed favorable dispersibility.
TABLE-US-00011 Silver nanowires 0.2 % by weight HPMC 0.4 % by
weight Sumirez 633 0.04 % by weight Triton X-100 0.004 % by weight
Water 99.356 % by weight
In addition, HPMC corresponded to 200 parts by weight based on 100
parts by weight of silver nanowires and Sumirez 633 corresponded to
10 parts by weight based on 100 parts by weight of HPMC.
[0190] A transparent conductive film was prepared according to
procedures similar to Example 1. The transparent conductive film
obtained had a surface resistance value of 31.4
.OMEGA./.quadrature., a total transmittance of 90.4% and a haze of
2.4%. Moreover, environmental resistance and process resistance
were favorable.
Example 12
Preparation of Aqueous Polymer Solution X
[0191] Then, 1.0 wt. % aqueous polymer solution X was prepared by
measuring 1.16 g of Elastron BN-11 (trade name) (having an
isocyanate group, Dai-Ichi Kogyo Seiyaku Co., Ltd.) having a solids
concentration of 34.5% by weight and diluting the mixture with 6.84
g of ultrapure water.
Preparation of a Coating Forming Composition
[0192] A coating forming composition having the following
composition was prepared according to procedures similar to Example
1 except that 1.0 wt. % aqueous polymer solution X was used as an
aqueous polymer solution. The prepared coating forming composition
showed favorable dispersibility.
TABLE-US-00012 Silver nanowires 0.2 % by weight HPMC 0.4 % by
weight Elastron BN-11 0.04 % by weight Triton X-100 0.004 % by
weight Water 99.356 % by weight
In addition, HPMC corresponded to 200 parts by weight based on 100
parts by weight of silver nanowires and Elastron B-11 corresponded
to 10 parts by weight based on 100 parts by weight of HPMC.
[0193] A transparent conductive film was prepared according to
procedures similar to Example 1. The transparent conductive film
obtained had a surface resistance value of 36.0
.OMEGA./.quadrature., a total transmittance of 91.1% and a haze of
5.9%. Moreover, environmental resistance and process resistance
were favorable.
Example 13
Preparation of Aqueous Polymer Solution XI
[0194] Then, 1.0 wt. % aqueous polymer solution XI was prepared by
measuring 1.75 g of Elastron H-3 (trade name) (having an isocyanate
group, Dai-Ichi Kogyo Seiyaku Co., Ltd.) having a solids
concentration of 22.9% by weight and diluting the mixture with 6.25
g of ultrapure water.
Preparation of a Coating Forming Composition
[0195] A coating forming composition having the following
composition was prepared according to procedures similar to Example
1 except that 1.0 wt. % aqueous polymer solution XI was used as an
aqueous polymer solution. The prepared coating forming composition
showed favorable dispersibility.
TABLE-US-00013 Silver nanowires 0.2 % by weight HPMC 0.4 % by
weight Elastron H-3 0.04 % by weight Triton X-100 0.004 % by weight
Water 99.356 % by weight
In addition, HPMC corresponded to 200 parts by weight based on 100
parts by weight of silver nanowires and Elastron H-3 corresponded
to 10 parts by weight based on 100 parts by weight of HPMC.
[0196] A transparent conductive film was prepared according to
procedures similar to Example 1. The transparent conductive film
obtained had a surface resistance value of 25.7
.OMEGA./.quadrature., a total transmittance of 88.3% and a haze of
3.8%. Moreover, environmental resistance and process resistance
were favorable.
Example 14
Preparation of Aqueous Polymer Solution XII
[0197] Then, 1.0 wt. % aqueous polymer solution XII was prepared by
measuring 1.84 g of Elastron H-38 (trade name) (having an
isocyanate group, Dai-Ichi Kogyo Seiyaku Co., Ltd.) having a solids
concentration of 21.7% by weight and diluting the mixture with 6.16
g of ultrapure water.
Preparation of a Coating Forming Composition
[0198] A coating forming composition having the following
composition was prepared according to procedures similar to Example
1 except that 1.0 wt. % aqueous polymer solution XII was used as an
aqueous polymer solution. The prepared coating forming composition
showed favorable dispersibility.
TABLE-US-00014 Silver nanowires 0.2 % by weight HPMC 0.4 % by
weight Elastron H-38 0.04 % by weight Triton X-100 0.004 % by
weight Water 99.356 % by weight
In addition, HPMC corresponded to 200 parts by weight based on 100
parts by weight of silver nanowires and Elastron H-38 corresponded
to 10 parts by weight based on 100 parts by weight of HPMC.
[0199] A transparent conductive film was prepared according to
procedures similar to Example 1. The transparent conductive film
obtained had a surface resistance value of 22.6
.OMEGA./.quadrature., a total transmittance of 87.9% and a haze of
5.0%. Moreover, environmental resistance and process resistance
were favorable.
Example 15
Preparation of Aqueous Polymer Solution XIII
[0200] Then, 1.0 wt. % aqueous polymer solution XIII was prepared
by measuring 0.08 g of Nikalac MW-22 (trade name) (having an
N-methylol ether group, Sanwa Chemical Co., Ltd.) having a solids
concentration of 100% by weight and diluting the mixture with 7.92
g of ultrapure water.
Preparation of a Coating Forming Composition
[0201] A coating forming composition having the following
composition was prepared according to procedures similar to Example
1 except that 4.00 g of 0.8 wt. % binder solution II was used as a
binder solution and 1.0 wt. % aqueous polymer solution XIII was
used as an aqueous polymer solution. The prepared coating forming
composition showed favorable dispersibility.
TABLE-US-00015 Silver nanowires 0.2 % by weight HPMC 0.4 % by
weight Nikalac MW-22 0.04 % by weight Triton X-100 0.004 % by
weight Water 99.356 % by weight
In addition, HPMC corresponded to 200 parts by weight based on 100
parts by weight of silver nanowires and Nikalac MW-22 corresponded
to 10 parts by weight based on 100 parts by weight of HPMC.
[0202] A transparent conductive film was prepared according to
procedures similar to Example 1 except that spin coating was
performed at 1,000 rpm. The transparent conductive film obtained
had a surface resistance value of 32.1 .OMEGA./.quadrature., a
total transmittance of 91.5% and a haze of 1.4%. Moreover,
environmental resistance and process resistance were favorable.
Example 16
[0203] A coating forming composition having the following
composition was prepared according to procedures similar to Example
15 except that an amount of 1.0 wt. % aqueous Nikalac MW-22
solution was changed to 0.08 g. The prepared coating forming
composition showed favorable dispersibility.
TABLE-US-00016 Silver nanowires 0.2 % by weight HPMC 0.4 % by
weight Nikalac MW-22 0.01 % by weight Triton X-100 0.004 % by
weight Water 99.386 % by weight
In addition, HPMC corresponded to 200 parts by weight based on 100
parts by weight of silver nanowires and Nikalac MW-22 corresponded
to 2.5 parts by weight based on 100 parts by weight of HPMC.
[0204] A transparent conductive film was prepared according to
procedures similar to Example 1 except that spin coating was
performed at 1,000 rpm. The transparent conductive film obtained
had a surface resistance value of 30.9 .OMEGA./.quadrature., a
total transmittance of 91.4% and a haze of 1.4%. Moreover,
environmental resistance and process resistance were favorable.
Example 17
[0205] A coating forming composition having the following
composition was prepared according to procedures similar to Example
15 except that an amount of 1.0 wt. % aqueous Nikalac MW-22
solution was changed to 1.28 g. The prepared coating forming
composition showed favorable dispersibility.
TABLE-US-00017 Silver nanowires 0.2 % by weight HPMC 0.4 % by
weight Nikalac MW-22 0.16 % by weight Triton X-100 0.004 % by
weight Water 99.236 % by weight
In addition, HPMC corresponded to 200 parts by weight based on 100
parts by weight of silver nanowires and Nikalac MW-22 corresponded
to 40 parts by weight based on 100 parts by weight of HPMC.
[0206] A transparent conductive film was prepared according to
procedures similar to Example 1 except that spin coating was
performed at 1,000 rpm. The transparent conductive film obtained
had a surface resistance value of 121 .OMEGA./.quadrature., a total
transmittance of 89.7% and a haze of 0.7%. Moreover, environmental
resistance and process resistance were favorable.
Example 18
[0207] A coating forming composition having the following
composition was prepared according to procedures similar to Example
1 except that 4.00 g of 0.8 wt. % binder solution IV was used as a
binder solution and 1.0 wt. % aqueous polymer solution XIII was
used as an aqueous polymer solution. The prepared coating forming
composition showed favorable dispersibility.
TABLE-US-00018 Silver nanowires 0.2 % by weight HPMC 0.4 % by
weight Nikalac MW-22 0.04 % by weight Triton X-100 0.004 % by
weight Water 99.356 % by weight
In addition, HPMC corresponded to 200 parts by weight based on 100
parts by weight of silver nanowires and Nikalac MW-22 corresponded
to 10 parts by weight based on 100 parts by weight of HPMC.
[0208] A transparent conductive film was prepared according to
procedures similar to Example 1 except that spin coating was
performed at 1,000 rpm. The transparent conductive film obtained
had a surface resistance value of 33.5 .OMEGA./.quadrature., a
total transmittance of 91.3% and a haze of 1.4%. Moreover,
environmental resistance and process resistance were favorable.
Example 19
Preparation of aqueous polymer solution XIV
[0209] Then, 1.0 wt. % aqueous polymer solution XIV was prepared by
measuring 0.114 g of Nikalac MW-30 (trade name) (having an
N-methylol ether group, Sanwa Chemical Co., Ltd.) having a solids
concentration of 100% by weight and diluting the mixture with 7.886
g of ultrapure water.
Preparation of a Coating Forming Composition
[0210] A coating forming composition having the following
composition was prepared according to procedures similar to Example
1 except that 4.00 g of 0.8 wt. % binder solution II was used as a
binder solution and 1.0 wt. % aqueous polymer solution XIV was used
as an aqueous polymer solution. The prepared coating forming
composition showed favorable dispersibility.
TABLE-US-00019 Silver nanowires 0.2 % by weight HPMC 0.4 % by
weight Nikalac MW-30 0.04 % by weight Triton X-100 0.004 % by
weight Water 99.356 % by weight
In addition, HPMC corresponded to 200 parts by weight based on 100
parts by weight of silver nanowires and Nikalac MW-30 corresponded
to 10 parts by weight based on 100 parts by weight of HPMC.
[0211] A transparent conductive film was prepared according to
procedures similar to Example 1 except that spin coating was
performed at 1,000 rpm. The transparent conductive film obtained
had a surface resistance value of 32.7 .OMEGA./.quadrature., a
total transmittance of 91.5% and a haze of 1.5%. Moreover,
environmental resistance and process resistance were favorable.
Example 20
Preparation of Aqueous Polymer Solution XV
[0212] Then, 1.0 wt. % aqueous polymer solution XV was prepared by
measuring 0.1143 g of Nikalac MX-035 (trade name) (having an
N-methylol ether group, Sanwa Chemical Co., Ltd.) having a solids
concentration of 100% by weight and diluting the mixture with
7.8857 g of ultrapure water.
Preparation of a Coating Forming Composition
[0213] A coating forming composition having the following
composition was prepared according to procedures similar to Example
1 except that 4.00 g of 0.8 wt. % binder solution II was used as a
binder solution and 1.0 wt. % aqueous polymer solution XV was used
as an aqueous polymer solution. The prepared coating forming
composition showed favorable dispersibility.
TABLE-US-00020 Silver nanowires 0.2 % by weight HPMC 0.4 % by
weight Nikalac MX-035 0.04 % by weight Triton X-100 0.004 % by
weight Water 99.356 % by weight
In addition, HPMC corresponded to 200 parts by weight based on 100
parts by weight of silver nanowires and Nikalac MX-035 corresponded
to 10 parts by weight based on 100 parts by weight of HPMC.
[0214] A transparent conductive film was prepared according to
procedures similar to Example 1 except that spin coating was
performed at 1,000 rpm. The transparent conductive film obtained
had a surface resistance value of 36.5 .OMEGA./.quadrature., a
total transmittance of 91.5% and a haze of 1.5%. Moreover,
environmental resistance and process resistance were favorable.
Example 21
Preparation of Aqueous Polymer Solution XVI
[0215] Then, 1.0 wt. % aqueous polymer solution XVI was prepared by
measuring 0.08 g of Nikalac MW-30 (trade name) (having an
N-methylol ether group, Sanwa Chemical Co., Ltd.) having a solids
concentration of 100% by weight and diluting the mixture with 7.92
g of isopropyl alcohol.
Preparation of a Coating Forming Composition
[0216] A coating forming composition having the following
composition was prepared according to procedures similar to Example
1 except that 4.00 g of 0.8 wt. % binder solution II was used as a
binder solution and 1.0 wt. % aqueous polymer solution XVI was used
as an aqueous polymer solution. The prepared coating forming
composition showed favorable dispersibility.
TABLE-US-00021 Silver nanowires 0.2 % by weight HPMC 0.4 % by
weight Nikalac MW-30 0.04 % by weight Triton X-100 0.004 % by
weight Water 95.356 % by weight Isopropyl alcohol 4 % by weight
In addition, HPMC corresponded to 200 parts by weight based on 100
parts by weight of silver nanowires and Nikalac MW-30 corresponded
to 10 parts by weight based on 100 parts by weight of HPMC.
[0217] A transparent conductive film was prepared according to
procedures similar to Example 1 except that spin coating was
performed at 1,000 rpm. The transparent conductive film obtained
had a surface resistance value of 33.7 .OMEGA./.quadrature., a
total transmittance of 91.5% and a haze of 1.4%. Moreover,
environmental resistance and process resistance were favorable.
Example 22
Preparation of Aqueous Polymer Solution XVII
[0218] Then, 1.0 wt. % aqueous polymer solution XVII was prepared
by measuring 0.114 g of Nikalac MW-22 having a solids concentration
of 100% by weight (trade name) (having an N-methylol ether group,
Sanwa Chemical Co., Ltd.) and diluting the mixture with 7.886 g of
isopropyl alcohol.
Preparation of a Coating Forming Composition
[0219] A coating forming composition having the following
composition was prepared according to procedures similar to Example
1 except that 4.00 g of 0.8 wt. % binder solution II was used as a
binder solution and 1.0 wt. % aqueous polymer solution XVII was
used as an aqueous polymer solution. The prepared coating forming
composition showed favorable dispersibility.
TABLE-US-00022 Silver nanowires 0.2 % by weight HPMC 0.4 % by
weight Nikalac MW-22 0.04 % by weight Triton X-100 0.004 % by
weight Water 95.356 % by weight Isopropyl alcohol 4 % by weight
In addition, HPMC corresponded to 200 parts by weight based on 100
parts by weight of silver nanowires and Nikalac MW-22 corresponded
to 10 parts by weight based on 100 parts by weight of HPMC.
[0220] A transparent conductive film was prepared according to
procedures similar to Example 1 except that spin coating was
performed at 1,000 rpm. The transparent conductive film obtained
had a surface resistance value of 33.1 .OMEGA./.quadrature., a
total transmittance of 91.5% and a haze of 1.4%. Moreover,
environmental resistance and process resistance were favorable.
Example 23
Preparation of Aqueous Polymer Solution XVIII
[0221] Then, 1.0 wt. % aqueous polymer solution XVIII was prepared
by measuring 0.1143 g of Nikalac MX-035 having a solids
concentration of 100% by weight (trade name) (having an N-methylol
ether group, Sanwa Chemical Co., Ltd.) and diluting the mixture
with 7.8857 g of isopropyl alcohol.
Preparation of a Coating Forming Composition
[0222] A coating forming composition having the following
composition was prepared according to procedures similar to Example
1 except that 4.00 g of 0.8 wt. % binder solution II was used as a
binder solution and 1.0 wt. % aqueous polymer solution XVIII was
used as an aqueous polymer solution. The prepared coating forming
composition showed favorable dispersibility.
TABLE-US-00023 Silver nanowires 0.2 % by weight HPMC 0.4 % by
weight Nikalac MX-035 0.04 % by weight Triton X-100 0.004 % by
weight Water 95.356 % by weight Isopropyl alcohol 4 % by weight
In addition, HPMC corresponded to 200 parts by weight based on 100
parts by weight of silver nanowires and Nikalac MX-035 corresponded
to 10 parts by weight based on 100 parts by weight of HPMC.
[0223] A transparent conductive film was prepared according to
procedures similar to Example 1 except that spin coating was
performed at 1,000 rpm. The transparent conductive film obtained
had a surface resistance value of 37.1 .OMEGA./.quadrature., a
total transmittance of 91.5% and a haze of 1.5%. Moreover,
environmental resistance and process resistance were favorable.
Example 24
Preparation of Aqueous Compound Solution I Having an Alkoxysilyl
Group (the Third Component)
[0224] Then, 0.5 wt. % aqueous solution I was prepared by measuring
0.1 g of Sila-Ace 5330 (trade name) (compound having an amino group
and an alkoxysilyl group, JNC Corporation) and diluting the mixture
with 19.9 g of ultrapure water.
Preparation of a Coating Forming Composition
[0225] A coating forming composition having the following
composition was prepared according to procedures similar to Example
1 except that 4.00 g of 0.8 wt. % binder solution II was used as a
binder solution and 0.5 wt. % aqueous solution I was used without
using aqueous polymer solution I. The prepared coating forming
composition showed favorable dispersibility.
TABLE-US-00024 Silver nanowires 0.2 % by weight HPMC 0.4 % by
weight Sila-Ace S330 0.04 % by weight Triton X-100 0.004 % by
weight Water 99.356 % by weight
In addition, HPMC corresponded to 200 parts by weight based on 100
parts by weight of silver nanowires and Sila-Ace S330 corresponded
to 10 parts by weight based on 100 parts by weight of HPMC.
[0226] A transparent conductive film was prepared according to
procedures similar to Example 1 except that spin coating was
performed at 1,000 rpm. The transparent conductive film obtained
had a surface resistance value of 36.4 .OMEGA./.quadrature., a
total transmittance of 91.1% and a haze of 1.5%. Moreover,
environmental resistance and process resistance were favorable.
Example 25
Preparation of Aqueous Compound Solution II Having an Alkoxysilyl
Group
[0227] Then, 0.5 wt. % aqueous solution II was prepared by
measuring 0.1 g of Sila-Ace 5510 (trade name) (compound having an
amino group and an alkoxysilyl group, JNC Corporation) and diluting
the mixture with 19.9 g of ultrapure water.
Preparation of a Coating Forming Composition
[0228] A coating forming composition having the following
composition was prepared according to procedures similar to Example
1 except that 4.00 g of 0.8 wt. % binder solution II was used as a
binder solution and 0.5 wt. % aqueous solution II was used without
using aqueous polymer solution I. The prepared coating forming
composition showed favorable dispersibility.
TABLE-US-00025 Silver nanowires 0.2 % by weight HPMC 0.4 % by
weight Sila-Ace S510 0.04 % by weight Triton X-100 0.004 % by
weight Water 99.356 % by weight
In addition, HPMC corresponded to 200 parts by weight based on 100
parts by weight of silver nanowires and Sila-Ace S510 corresponded
to 10 parts by weight based on 100 parts by weight of HPMC.
[0229] A transparent conductive film was prepared according to
procedures similar to Example 1 except that spin coating was
performed at 1,000 rpm. The transparent conductive film obtained
had a surface resistance value of 34.8 .OMEGA./.quadrature., a
total transmittance of 91.4% and a haze of 1.6%. Moreover,
environmental resistance and process resistance were favorable.
Example 26
Preparation of Aqueous Compound Solution III Having an Alkoxysilyl
Group
[0230] Then, 0.5 wt. % aqueous solution III was prepared by
measuring 0.1 g of 1,2-bis(trimethoxysilyl)ethane (compound having
alkoxysilyl groups at both ends, made by Tokyo Kasei Kogyo Co.,
Ltd.) and diluting the mixture with 19.9 g of ultrapure water.
Preparation of a Coating Forming Composition
[0231] A coating forming composition having the following
composition was prepared according to procedures similar to Example
1 except that 4.00 g of 0.8 wt. % binder solution II was used as a
binder solution and 0.5 wt. % aqueous solution III was used without
using aqueous polymer solution I. The prepared coating forming
composition showed favorable dispersibility.
TABLE-US-00026 Silver nanowires 0.2 % by weight HPMC 0.4 % by
weight 1,2-Bis(trimethoxysilyl)ethane 0.04 % by weight Triton X-100
0.004 % by weight Water 99.356 % by weight
In addition, HPMC corresponded to 200 parts by weight based on 100
parts by weight of silver nanowires and
1,2-bis(trimethoxysilyl)ethane corresponded to 10 parts by weight
based on 100 parts by weight of HPMC.
[0232] A transparent conductive film was prepared according to
procedures similar to Example 1 except that spin coating was
performed at 1,000 rpm. The transparent conductive film obtained
had a surface resistance value of 36.8 .OMEGA./.quadrature., a
total transmittance of 91.3% and a haze of 1.5%. Moreover,
environmental resistance and process resistance were favorable.
Example 27
[0233] A coating forming composition having the following
composition was prepared according to procedures similar to Example
1 except that 4.00 g of 0.8 wt. % binder solution II was used as a
binder solution and 0.5 wt. % aqueous solution I was added. The
prepared coating forming composition showed favorable
dispersibility.
TABLE-US-00027 Silver nanowires 0.2 % by weight HPMC 0.4 % by
weight Riken Resin MM-35 0.04 % by weight Riken Fixer RC-3 0.004 %
by weight Sila-Ace S330 0.04 % by weight Triton X-100 0.004 % by
weight Water 99.312 % by weight
In addition, HPMC corresponded to 200 parts by weight based on 100
parts by weight of silver nanowires and Sila-Ace 5330 corresponded
to 10 parts by weight based on 100 parts by weight of HPMC.
[0234] A transparent conductive film was prepared according to
procedures similar to Example 1 except that spin coating was
performed at 1,000 rpm. The transparent conductive film obtained
had a surface resistance value of 35.8 .OMEGA./.quadrature., a
total transmittance of 91.0% and a haze of 1.7%. Moreover,
environmental resistance and process resistance were favorable.
Example 28
[0235] A coating forming composition having the following
composition was prepared according to procedures similar to Example
1 except that 4.00 g of 0.8 wt. % binder solution II was used as a
binder solution and 0.5 wt. % aqueous solution II was added. The
prepared coating forming composition showed favorable
dispersibility.
TABLE-US-00028 Silver nanowires 0.2 % by weight HPMC 0.4 % by
weight Riken Resin MM-35 0.04 % by weight Riken Fixer RC-3 0.004 %
by weight Sila-Ace S510 0.04 % by weight Triton X-100 0.004 % by
weight Water 99.312 % by weight
In addition, HPMC corresponded to 200 parts by weight based on 100
parts by weight of silver nanowires and Sila-Ace 5510 corresponded
to 10 parts by weight based on 100 parts by weight of HPMC.
[0236] A transparent conductive film was prepared according to
procedures similar to Example 1 except that spin coating was
performed at 1,000 rpm. The transparent conductive film obtained
had a surface resistance value of 36.3 .OMEGA./.quadrature., a
total transmittance of 91.0% and a haze of 1.7%. Moreover,
environmental resistance and process resistance were favorable.
Example 29
[0237] A coating forming composition having the following
composition was prepared according to procedures similar to Example
1 except that 4.00 g of 0.8 wt. % binder solution II was used as a
binder solution and 0.5 wt. % aqueous solution III was used. The
prepared coating forming composition showed favorable
dispersibility.
TABLE-US-00029 Silver nanowires 0.2 % by weight HPMC 0.4 % by
weight 1,2-Bis(trimethoxysilyl)ethane 0.04 % by weight Triton X-100
0.004 % by weight Water 99.356 % by weight
In addition, HPMC corresponded to 200 parts by weight based on 100
parts by weight of silver nanowires and
1,2-bis(trimethoxysilyl)ethane corresponded to 10 parts by weight
based on 100 parts by weight of HPMC.
[0238] A transparent conductive film was prepared according to
procedures similar to Example 1 except that spin coating was
performed at 1,000 rpm. The transparent conductive film obtained
had a surface resistance value of 35.3 .OMEGA./.quadrature., a
total transmittance of 91.1% and a haze of 1.7%. Moreover,
environmental resistance and process resistance were favorable.
Example 30
[0239] A coating forming composition having the following
composition was prepared according to procedures similar to Example
1 except that 4.00 g of 0.8 wt. % binder solution II was used as a
binder solution and 0.16 g of 0.5 wt. % aqueous solution I was used
without using aqueous polymer solution I. The prepared coating
forming composition showed favorable dispersibility.
TABLE-US-00030 Silver nanowires 0.2 % by weight HPMC 0.4 % by
weight Sila-Ace S330 0.02 % by weight Triton X-100 0.004 % by
weight Water 99.376 % by weight
In addition, HPMC corresponded to 200 parts by weight based on 100
parts by weight of silver nanowires and Sila-Ace 5330 corresponded
to 5 parts by weight based on 100 parts by weight of HPMC.
[0240] A transparent conductive film was prepared according to
procedures similar to Example 1 except that spin coating was
performed at 1,000 rpm. The transparent conductive film obtained
had a surface resistance value of 34.0 .OMEGA./.quadrature., a
total transmittance of 91.0% and a haze of 1.7%. Moreover,
environmental resistance and process resistance were favorable.
Example 31
[0241] A coating forming composition having the following
composition was prepared according to procedures similar to Example
1 except that 4.00 g of 0.8 wt. % binder solution II was used as a
binder solution and 0.08 g of 0.5 wt. % aqueous solution I was used
without using aqueous polymer solution I. The prepared coating
forming composition showed favorable dispersibility.
TABLE-US-00031 Silver nanowires 0.2 % by weight HPMC 0.4 % by
weight Sila-Ace S330 0.01 % by weight Triton X-100 0.004 % by
weight Water 99.386 % by weight
In addition, HPMC corresponded to 200 parts by weight based on 100
parts by weight of silver nanowires and Sila-Ace 5330 corresponded
to 2.5 parts by weight based on 100 parts by weight of HPMC.
[0242] A transparent conductive film was prepared according to
procedures similar to Example 1 except that spin coating was
performed at 4,000 rpm. The transparent conductive film obtained
had a surface resistance value of 65.0 .OMEGA./.quadrature., a
total transmittance of 93.0% and a haze of 0.7%. Moreover,
environmental resistance and process resistance were favorable.
Example 32
Patterning of a Transparent Conductive Film
[0243] On the transparent conductive film prepared according to
Example 1, 1 mL of ZPP-1700PG (trade name) (Nippon Zeon Co., Ltd.)
being a positive photoresist was dropped and spin coating was
performed at 4,000 rpm using a spin coater. The glass substrate was
calcinated on a hot stage at 100.degree. C. for 90 seconds. A UV
light was irradiated on the photoresist from above under conditions
of 50 mJ/cm.sup.2 through a chromium-deposited photomask using an
exposure system (HB-20201CL model, extra high voltage mercury lamp
as a light source, USH-2004To model, Ushio, Inc.). A coating after
UV irradiation was immersed into a 2.38 wt. % aqueous
tetramethylammonium hydroxide solution (trade name; TMA-208, Kanto
Chemical Co., Inc.) for 30 seconds, an exposed part was removed,
and thus development was performed. A coating after a development
operation was immersed into Al etching solution (trade name) (Kanto
Chemical Co., Inc.) for 30 seconds, and thus exposed silver
nanowires in a transparent conductive film was etched. The
photoresist was removed by immersing a coating after etching into
acetone for 2 minutes. Dry air was blown onto the coating and the
substrate using an air gun, and thus drying was performed.
[0244] Observation was performed using an incident-light darkfield
microscope having a magnification of 500 times. A dot-line-space
having a diameter or width of 5 micrometers was formed. Moreover,
neither absence nor peeling of patterns was observed, and
patterning was favorably performed.
Example 33
Confirmation of a Margin of Patterning
[0245] Patterning of a transparent conductive film was performed
according to a composition and procedures similar to Example 32
except that immersion time into the Al etching solution was changed
to 15, 30, 45, 60, 90, 120, 180, and 300 seconds. Observation was
performed using an incident-light darkfield microscope having a
magnification of 500 times. A dot-line-space and a reverse pattern
having a diameter or width of 5 micrometers were formed under any
conditions. Moreover, neither absence nor peeling of patterns was
observed on the transparent conductive film, and patterning was
favorably performed.
Comparative Example 1
[0246] A coating forming composition as described in Example 17 of
WO 2008/046058 A was prepared according the procedures as described
below. In addition, a component amount was appropriately determined
so as to show a desired surface resistance. A coating forming
composition having the following composition was obtained by
measuring 4.00 g of 0.8 wt. % binder solution I, 1.60 g of 1.0 wt.
% aqueous silver nanowires dispersion solution and 2.40 g of
ultrapure water, and agitated until a uniform solution was formed.
The prepared coating forming composition had a viscosity of 56
mPas, and showed a favorable dispersibility even after 1 week.
TABLE-US-00032 Silver nanowires 0.2 % by weight HPMC 0.4 % by
weight Triton X-100 0.004 % by weight Water 99.396 % by weight
In addition, HPMC corresponded to 200 parts by weight based on 100
parts by weight of silver nanowires.
[0247] A transparent conductive film was prepared according to
procedures similar to Example 1. The transparent conductive film
obtained had a surface resistance value of 48.2
.OMEGA./.quadrature., a total transmittance of 92.0% and a haze of
1.3%. Moreover, environmental resistance, process resistance and
close contact were not sufficient, and inferior to the coating
forming composition according to the present invention.
Furthermore, the environmental resistance, the process resistance
and the close contact were not sufficient even on silicon nitride
and an overcoat (product name; PIG-7424, JNC Corporation), and
inferior to the coating forming composition according to the
present invention.
[0248] The environmental resistance, the process resistance and the
close contact were confirmed to be poor because a component
constitution in Comparative Example 2 was different from the
coating forming composition of the present invention.
Comparative Example 2
[0249] According to JP 2010-205532 A, a film of silver nanowires
and a crosslinkable compound was formed in a first layer, and a
film of an organic conductive material was formed in a second
layer. The film of the first layer as described in Preparation of
Transparent Electrode 108 in Example of JP 2010-205532 A was formed
according to the procedures as described below.
[0250] Thus, 3.20 g of an aqueous solution of PVA 203 (trade name)
(Kuraray Co., Ltd., 3.4 mPas in viscosity of a 4 wt. % aqueous
solution) that was diluted to 1.0 wt. %, 0.32 g of 0.1 wt % aqueous
Triton X-100 solution, and 2.48 g of ultrapure water were measured,
and agitated until a uniform solution was formed. Then, 1.60 g of
1.0 wt. % aqueous silver nanowires dispersion solution was added,
and agitated until a uniform solution was formed. Furthermore, 0.40
g of an aqueous solution of glyoxal (Wako Pure Chemical Industries,
Ltd.) that was diluted to 0.1 wt. % was added, agitated until a
uniform solution was formed, and thus a coating forming composition
having the following composition was obtained. As for the prepared
coating forming composition, precipitates of silver nanowires were
observed on a bottom of a screw vial after 1 week, and
dispersibility was poor.
TABLE-US-00033 Silver nanowires 0.2 % by weight PVA 203 0.05 % by
weight Glyoxal 0.005 % by weight Triton X-100 0.004 % by weight
Water 99.741 % by weight
In addition, PVA 203 corresponded to 25 parts by weight based on
100 parts by weight of silver nanowires and glyoxal corresponded to
10 parts by weight based on 100 parts by weight of PVA 203.
[0251] A transparent conductive film was prepared according to
procedures similar to Example 1. The transparent conductive film
obtained had a surface resistance value of 150
.OMEGA./.quadrature., a total transmittance of 92.3% and a haze of
0.9%. Moreover, environmental resistance, process resistance and
close contact were poor.
[0252] The environmental resistance, the process resistance and the
close contact were confirmed to be poor because a component
constitution in Comparative Example 2 was different from the
coating forming composition of the present invention.
Comparative Example 3
[0253] According to JP 2010-205532 A, a film of silver nanowires
and a crosslinkable compound was formed in a first layer, and a
film of an organic conductive material was formed in a second
layer. The film of the first layer as described in Preparation of
Transparent Electrode 113 in Example of JP 2010-205532 A was formed
according to the procedures as described below.
[0254] Thus, 3.20 g of an aqueous solution of PVA 203 (trade name)
(Kuraray Co., Ltd., 3.4 mPas in viscosity of a 4 wt. % aqueous
solution) that was diluted to 1.0 wt. %, 0.32 g of 0.1 wt. %
aqueous Triton X-100 solution, and 2.48 g of ultrapure water were
measured, and agitated until a uniform solution was formed. Then,
1.60 g of 1.0 wt. % aqueous silver nanowires dispersion solution
was added, and agitated until a uniform solution was formed.
Furthermore, 0.40 g of aqueous Riken Resin MM-35 solution diluted
to 0.1 wt. o, and 0.40 g of aqueous Riken Fixer RC-3 solution
diluted to 0.1 wt. % were added, agitated until becoming uniform,
and thus a coating forming composition having the following
composition was obtained. As for the prepared coating forming
composition, precipitates of silver nanowires were observed on a
bottom of a screw vial after 1 week, and dispersibility was
poor.
TABLE-US-00034 Silver nanowires 0.2 % by weight PVA 203 0.05 % by
weight Riken Resin MM-35 0.005 % by weight Riken Fixer RC-3 0.005 %
by weight Triton X-100 0.004 % by weight Water 99.736 % by
weight
In addition, PVA 203 corresponded to 25 parts by weight based on
100 parts by weight of silver nanowires, Riken Resin MM-35
corresponded to 10 parts by weight based on 100 parts by weight of
PVA 203, and Riken Fixer RC-3 corresponded to 100 parts by weight
based on 100 parts by weight of Riken Resin MM-35.
[0255] A transparent conductive film was prepared according to
procedures similar to Example 1. As for the prepared coating
forming composition, precipitates of silver nanowires were observed
on a bottom of a screw vial after 1 week, and dispersibility was
poor. The transparent conductive film obtained had a surface
resistance value of 142 .OMEGA./.quadrature., a total transmittance
of 93.0% and a haze of 0.6%. Moreover, environmental resistance,
process resistance and close contact were poor.
[0256] The environmental resistance, the process resistance and the
close contact were confirmed to be poor because a component
constitution in Comparative Example 2 was different from the
coating forming composition of the present invention.
Comparative Example 4
Confirmation of a Margin of Patterning
[0257] Patterning of a transparent conductive film was performed in
a manner similar to Example 33 except that the coating forming
composition prepared in Comparative Example 1 was used. Observation
was performed using an incident-light darkfield microscope having a
magnification of 500 times. When immersion time into Al etching
solution was 15 or 30 seconds, a dot-line-space and a reverse
pattern having a diameter or width of 5 micrometers were formed.
When the immersion time into Al etching solution was 45 seconds or
more, a diameter or width of a pattern decreased in proportion to
the immersion time, a diameter or width of the reverse pattern
increased in proportion to the immersion time, and thus the coating
forming composition of the present invention was confirmed to have
a broader margin of patterning.
TABLE-US-00035 TABLE 1 Conduc- tivity Surface Transparency Envi-
resis- Total ron- Disper- tance transmit- mental Proces Sample
sibil- value tance Haze resis- resis- name ity
(.OMEGA./.quadrature.) (%) (%) tance tance Example 1 Good 47.4 91.4
1.6 Good Excellent Example 2 Good 43.9 91.3 1.6 Good Good Example 3
Good 103 89.3 0.8 Good Excellent Example 4 Good 30.8 91.2 1.7 Good
Excellent Example 5 Good 29.8 91.2 1.8 Good Excellent Example 6
Good 60.3 92.0 1.3 Good Good Example 7 Good 33.8 91.8 1.3 Good
Excellent Example 8 Good 51.1 91.3 1.6 Good Excellent Example 9
Good 52.8 91.2 1.5 Good Excellent Example 10 Good 54.0 91.4 1.5
Good Excellent Example 11 Good 31.4 90.4 2.4 Good Good Example 12
Good 36.0 91.1 5.9 Good Excellent Example 13 Good 25.7 88.3 3.8
Good Good Example 14 Good 22.6 87.9 5.0 Good Excellent Example 15
Good 32.1 91.5 1.4 Good Excellent Example 16 Good 30.9 91.4 1.4
Good Good Example 17 Good 121 89.7 0.7 Good Excellent Example 18
Good 33.5 91.5 1.4 Good Excellent Example 19 Good 32.7 91.5 1.5
Good Excellent Example 20 Good 36.5 91.5 1.5 Good Excellent Example
21 Good 33.7 91.5 1.4 Good Excellent Example 22 Good 33.1 91.5 1.4
Good Excellent Example 23 Good 37.1 91.5 1.5 Good Excellent Example
24 Good 36.4 91.1 1.5 Good Excellent Example 25 Good 34.8 91.4 1.6
Good Excellent Example 26 Good 36.8 91.3 1.5 Good Excellent Example
27 Good 35.8 91.0 1.7 Good Excellent Example 28 Good 36.3 91.0 1.7
Good Excellent Example 29 Good 35.3 91.1 1.7 Good Excellent Example
30 Good 34.0 91.0 1.7 Good Excellent Example 31 Good 65.0 93.0 0.7
Good Excellent Comparative Good 48.2 92.0 1.3 Mar- Bad Example 1
ginal Comparative Bad 150 92.3 0.9 Bad Bad Example 2 Comparative
Bad 142 93.0 0.6 Mar- Bad Example 3 ginal
INDUSTRIAL APPLICABILITY
[0258] A coating forming composition of the present invention can
be used in a process for manufacturing a device element such as a
liquid crystal display element, an organic electroluminescence
element, an electronic paper, a touch panel element and a
photovoltaic cell element. Moreover, a transparent conductive film
of the present invention is excellent in conductivity, optical
transparency, environmental resistance, process resistance and
close contact, and has a low surface resistance value and favorable
optical properties such as a favorable transmittance as well.
[0259] Although the present invention has been described and
illustrated with a certain degree of particularity, it is
understood that the disclosure has been made only by way of
example, and that numerous changes in the conditions and order of
steps can be resorted to by those skilled in the art without
departing from the spirit and scope of the invention.
* * * * *